CN114761449A

CN114761449A - Catalyst and process for producing the same

Info

Publication number: CN114761449A
Application number: CN202080082190.XA
Authority: CN
Inventors: L·M·C·雷斯科尼; S·施瓦曾伯格; V·维库嫩; A·列兹尼琴科; V·V·伊兹迈尔; D·S·科诺诺维奇; A·Z·沃斯科博尼克弗
Original assignee: Borealis AG
Current assignee: Borealis AG
Priority date: 2019-09-25
Filing date: 2020-09-25
Publication date: 2022-07-15
Anticipated expiration: 2040-09-25
Also published as: WO2021058740A1; US20220356274A1; CN114761450A; KR20220069073A; WO2021058742A1; JP2022549848A; US20230002605A1; EP4034579A1; CN114761449B; EP4034580A1

Abstract

A metallocene complex represented by the formula (I): each X is a sigma-ligand; at R₂In the Si-group, at least one R is methyl or ethyl and the other R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl, pentyl, hexyl, cyclohexyl and phenyl; each R¹Independently of each otherIs or may be different and is CH₂‑R⁷Group (I) wherein R⁷Is H or straight or branched C_1‑6Alkyl radical, C_3‑8Cycloalkyl or C_6‑10An aryl group; each R²Independently is-CH ═, -CY ═ CH₂-, -CHY-or-CY₂A radical in which Y is C_1‑6Hydrocarbyl and wherein n is 2-6; each R³And R⁴Independently are the same or can be different and are hydrogen, straight-chain or branched C_1‑6Alkyl radical, C_7‑20Aralkyl radical, C_7‑20Alkylaryl group, C_6‑20Aryl or-OY radicals, in which Y is C_1‑6A hydrocarbyl group; r⁵Is straight chain or branched C_1‑6Alkyl radical, C_7‑20Aralkyl radical, C_7‑20Alkylaryl or C_6‑20An aryl group; and R⁶Is C (R)⁸)₃Group, R⁸Is straight chain or branched C_1‑6An alkyl group; (A) wherein each phenyl group has at least one R³And at least one R⁴Is not hydrogen, and wherein at least one R is per phenyl group³And at least one R⁴Is hydrogen; or (B) one of R³Is an-OY group wherein Y is C_1‑6A hydrocarbon radical, in the 4-position of each phenyl radical, the other two R³The group is tert-butyl; and/or (C) one of R ⁴Is an-OY group wherein Y is C_1‑6A hydrocarbyl radical, in the 4-position of the phenyl ring, of which two R are additionally present⁴The group is tert-butyl.

Description

Catalyst and process for producing the same

The present invention relates to novel bis-indenyl ligands, complexes thereof and compositions comprising theseA catalyst for the complex. The invention also relates to the use of the novel bis-indenyl metallocene catalysts for producing heterophasic polypropylene copolymers, in particular polypropylene copolymers having a high molecular weight ethylene-propylene rubber component and a matrix component having a high melting point. The invention further relates to a synthetic process for preparing metallocene complexes which improve C₁Isolated yield of the desired trans isomer of the symmetrical metallocene.

Background

Metallocene catalysts have been used for many years to produce polyolefins. Numerous academic and patent publications describe the use of these catalysts in the polymerization of olefins. Metallocenes are now used in industry, in particular polyethylene and polypropylene are generally produced using cyclopentadienyl-based catalyst systems with different substitutions.

These metallocenes are commonly used to prepare polypropylene, such as isotactic polypropylene. The structure of metallocenes has been optimized to produce high molecular weight isotactic polypropylene, but its molecular weight capability is generally limited when producing heterophasic polypropylene with ethylene-propylene copolymers in the gas phase. It is known that for a given rubber comonomer composition, the tensile and impact properties of heterophasic polypropylenes can be improved by increasing the molecular weight of the rubber phase (e.g. as described in j.appl.polym.sci.2002, vol.85, pp.2412-2418 and j.appl.polym.sci.2003, vol.87, pp.1702-1712). However, in general, the ethylene-propylene rubber has a molecular weight of less than 4dL/g (measured as intrinsic viscosity, IV) _EPR) Measured in decalin (decalin) at 135 ℃.

Furthermore, metallocene catalysts that may be used to prepare heterophasic polypropylenes tend to produce homopolymer matrices (and hence heterophasic polypropylene polymers as a whole) with relatively low melting points (Tm), typically below 155 to 157 ℃. It is well known that higher Tm values favor the stiffness of the material. The combination of the high melting point of the homopolymer matrix (or of the heterophasic polypropylene itself) and the high molecular weight in the EPR rubber component is particularly desirable.

In this regard, heterophasic polypropylenes are polypropylenes comprising a propylene homopolymer matrix (or a propylene copolymer matrix with a low comonomer content, i.e. a random propylene copolymer) and a propylene ethylene (or propylene-ethylene-1-butene) rubber component, usually dispersed in the matrix.

The present inventors have developed a new catalyst which is capable of forming heterophasic polypropylene polymers with high matrix melting point and high molecular weight in the EPR component. The metallocene complex of the invention is an asymmetric hafnium bridged bis-indenyl type structure. Some of the metallocenes disclosed in the prior art have some similarities to the present invention.

C₂Symmetrical metallocenes are disclosed in WO 2007/116034. This document reports, inter alia, metallocene rac-Me ₂Si(2-Me-4-Ph-5-OMe-6-tBuInd)₂ZrCl₂And the metallocene is used as a polymerization catalyst after MAO activation for propylene homopolymerization and copolymerization of propylene with ethylene and higher alpha-olefins in solution polymerization. The resulting polymer IV was about 3 to 3.4dL/g as measured in Tetralin (THN) at 135 ℃. The IV value measured in decalin was about 20% higher than that measured in THN.

WO2006/097497 describes, inter alia, silica-supported rac-Me₂Si (2-methyl-4-phenyl-1, 5,6, 7-tetrahydro-s-indacen-1-yl)₂ZrCl₂And their use in the homo-and copolymerization of propylene with ethylene. The resulting polymer has an IV of about 3 to 3.4dL/g as measured in THN at 135 ℃.

WO2006/100258 describes the preparation of heterophasic polypropylene using pseudo-racemic dimethylsilanediyl- (6-methyl-4- (4 '-tert-butylphenyl) -1,2,3, 5-tetrahydro-s-indacen-7-yl) (2-isopropyl-4- (4' -tert-butylphenyl) -1-indenyl) -zirconium dichloride, but low IVs values are also reported.

EP2072546 describes the synthesis of heterophasic polypropylene using unsupported asymmetric metallocene dimethylsilyl [ (2-methyl- (4 '-tert-butyl) -4-phenyl-indenyl) (2-isopropyl- (4' -tert-butyl) -4-phenyl-indenyl) ] zirconium dichloride. The highest IV of EPRs measured in decalin at 135 ℃ was reported to be 3.4 dL/g.

EP2072584 describes the synthesis of heterophasic polypropylene using unsupported asymmetric metallocene dimethylsilyl [ (2-methyl- (4 '-tert-butyl) -4-phenyl-indenyl) (2-isopropyl- (4' -tert-butyl) -4-phenyl-indenyl) ] zirconium dichloride. The highest IV for EPRs measured in decalin at 135 ℃ was reported to be 2 dL/g.

The following table lists a number of known metallocene catalyst complexes:

IV of the above metallocene structure_EPRThe value was 3.4dL/g, measured in decalin at 135 ℃.

WO2016/038210 and WO2016/038211 also describe the polymerization of heterophasic polypropylene, such as rac-dimethylsilylene-bis (6-tert-butyl-2-isobutyl-5-methoxy-4-phenyl-1H-inden-1-yl) zirconium dichloride. IV_EPRLower values, such as 3.0dL/g or lower.

In EP2829558, the use of borate co-activators in unsupported single-site catalysts shows that borate co-activators have an adverse effect on the molecular weight of the rubber.

The inventors sought higher IV in the EPR phase of heterophasic PP. The molecular weight of the rubber (Mw,_EPR) The most important variable of (a) is the metallocene ligand structure (defining the intrinsic molecular weight capability of the catalyst). However, other factors may contribute to high IV values. Other factors include:

1. internal temperature T of polymerization reactor _P(T_PThe higher the Mw, the more the Mw,_EPRthe lower the height)

2. Partial pressure (concentration) of comonomer in the gas phase reactor (the higher the monomer concentration, Mw,_EPRthe higher the

3. Gas-phase comonomer ratio (i.e., the ratio of C2/C3 in the gas-phase reactor which determines the rubber content)

4. Amount of hydrogen taken from bulk (loop) reactor or intentionally added to subsequent reactor

5. Type of activator (e.g., methylaluminoxane, borate, or combination thereof)

Variables 1-4 are process variables, but variables 5 and the nature of the catalyst ingredients can be preselected.

We have found that, surprisingly, the use of the metallocenes of the inventionThe metal complexes enable the preparation of heterophasic polypropylene copolymers wherein the EPR component has a higher molecular weight (higher IV) than previously observed_EPR). The resulting heterophasic polypropylene copolymers have excellent tensile and impact properties.

As regards the method of synthesis of metallocenes, the racemoselectivity of metallocenes of group 4 (in the bis-indenyl C)₁Anti-racemoselectivity in the case of symmetric complexes) synthesis.

The first involves modification of the transition metal salt used in the metallization step. While increasing the final yield of the desired metallocene isomer, this process adds several steps to an already complex synthetic scheme. Examples of such methods are described in, for example, WO1999/015538, WO2004/037840, US7098354 and WO 2005/108408.

The second method is to decompose the undesired isomer. While facilitating the separation of the desired isomer, this approach actually reduces the overall yield compared to standard synthetic methods due to non-completely selective decomposition. Several documents describe such a method, for example EP 819695.

The third method uses R₄NBr as epimer. For example, US7465688 discloses R₄The use of NBr in specific metallocenes and solvents is adjusted to increase the yield of the desired isomer for these specific metallocenes. However, the applied temperature is rather high.

A fourth process, described in WO1998/020014, uses THF as the epimerisation medium and maintains a slurry of bridged zirconocene and THF at a temperature ranging from 20 to 120 ℃ for 1 to 12 hours. However, the desired trans isomer cannot be obtained in very high yields by this method.

The invention also relates to a process for the preparation of the desired trans isomer, especially the desired racemic trans isomer, more especially C₁-a novel process for maximizing the content of the desired racemic trans isomer in symmetric metallocene complexes.

Disclosure of Invention

Viewed from one aspect the present invention provides a metallocene complex represented by formula (I):

each X is a sigma-ligand (sigma-ligand);

At R₂In the Si-group, at least one R is methyl or ethyl and the other R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl, pentyl, hexyl, cyclohexyl and phenyl;

each R¹Independently are the same or may be different and are CH₂-R⁷Group (I) wherein R⁷Is H or straight or branched C_1-6Alkyl radical, C_3-8Cycloalkyl or C_6-10An aryl group;

each R²Independently is-CH ═, -CY ═ CH₂-, -CHY-or-CY₂A radical in which Y is C_1-6Hydrocarbyl and wherein n is 2-6;

each R³And R⁴Independently are the same or can be different and are hydrogen, straight-chain or branched C_1-6Alkyl radical, C_7-20Aralkyl radical, C_7-20Alkylaryl group, C_6-20Aryl or-OY radicals, in which Y is C_1-6A hydrocarbyl group;

R⁵is straight chain or branched C_1-6Alkyl radical, C_7-20Aralkyl, C_7-20Alkylaryl or C_6-20An aryl group; and

R⁶is C (R)⁸)₃Group, R⁸Is straight chain or branched C_1-6An alkyl group;

(A) wherein each phenyl group has at least one R³And at least one R⁴Is not hydrogen, and wherein at least one R is per phenyl group³And at least one R⁴Is hydrogen; or

(B) Wherein one R is³Is an-OY group wherein Y is C_1-6A hydrocarbon radical, in the 4-position of each phenyl radical, the other two R³The group is tert-butyl; and/or

(C) Wherein one R is⁴Is an-OY group wherein Y is C_1-6A hydrocarbon radical, in the 4-position of the phenyl ring, two further R ⁴The group is tert-butyl.

Viewed from another aspect the invention provides a catalyst comprising

(i) A metallocene complex of formula (I) as hereinbefore defined; and

(ii) a cocatalyst comprising a compound of a group 13 element.

The catalysts of the invention can be used in unsupported or solid form. The catalysts of the invention can be used as homogeneous catalysts or heterogeneous catalysts. The catalyst of the invention, in solid form, preferably in the form of solid particles, may be supported on an external support material, for example silica or alumina or a mixed oxide such as silica-alumina, or in one embodiment, is free of an external support, but still in solid form, as described in WO 2003/051934.

Thus, viewed from a further aspect the invention provides a catalyst comprising

(i) A metallocene complex of formula (I) as hereinbefore defined;

(ii) a cocatalyst comprising a compound of a group 13 element; and

(iii) a silica support.

Viewed from a further aspect the invention provides the use in the polymerisation of propylene, in particular in the preparation of a heterophasic polypropylene copolymer of a catalyst as hereinbefore defined.

Viewed from a further aspect the invention provides a process for the polymerisation of propylene using a catalyst as hereinbefore described comprising reacting propylene and optionally a comonomer, particularly ethylene and/or 1-butene, with a catalyst as hereinbefore described.

More specifically, the present invention comprises a process for the preparation of a heterophasic propylene ethylene copolymer or heterophasic propylene ethylene 1-butene copolymer comprising:

(I) polymerizing propylene and optionally ethylene and/or 1-butene in the presence of a catalyst according to the invention to form:

a1) a Crystalline Fraction (CF) comprising a propylene homopolymer or a propylene copolymer with ethylene and/or 1-butene having up to 2 wt% of a comonomer as the matrix component; and

(II) subsequently polymerising additional propylene and ethylene and optionally 1-butene, preferably in the gas phase, in the presence of the matrix component of step (I), to form:

a2) a propylene-ethylene copolymer or propylene-ethylene-1-butene copolymer Soluble Fraction (SF) having a comonomer content of from 12 to 85% by weight, preferably from 15.0 to 70.0% by weight;

wherein the Crystalline Fraction (CF) represents from 30.0 to 95.0% by weight of the heterophasic propylene-ethylene copolymer or heterophasic propylene-ethylene-1-butene copolymer, the Soluble Fraction (SF) represents from 5.0 to 70.0% by weight,

wherein the amount of Crystalline Fraction (CF) and the amount of Soluble Fraction (SF) are determined in 1,2, 4-trichlorobenzene at 40 ℃; and wherein

The intrinsic viscosity IV (SF) of the Soluble Fraction (SF) of the heterophasic propylene-ethylene copolymer or heterophasic propylene-ethylene-1-butene copolymer in decalin at 135 deg.C is in the range of 1,5 to 10dl/g, preferably 2 to 9dl/g, more preferably 4.5 to 9.0dl/g, most preferably 5.5 to 8.0 dl/g.

Preferably the comonomer is ethylene alone.

The invention further relates to a synthesis process for the production of metallocene complexes with improved isolated yield of the desired trans isomer, in particular C₁-symmetrical metallocene complexes.

Definition of

Throughout the description, the following definitions are used:

the term "C_1-20Hydrocarbyl "including C_1-20Alkyl radical, C_2-20Alkenyl radical, C_2-20Alkynyl, C_3-20Cycloalkyl radical, C_3-20Cycloalkenyl radical, C_6-20Aryl radical, C_7-20Alkylaryl or C_7-20Aralkyl groups or mixtures of these groups, for example cycloalkyl groups substituted with alkyl groups. The linear and branched hydrocarbon groups must not contain cyclic units. The aliphatic hydrocarbon group must not contain an aromatic ring.

Preferred C unless otherwise stated_1-20The hydrocarbon radical being C_1-20Alkyl radical, C_4-20Cycloalkyl radical, C_5-20Cycloalkyl-alkyl, C_7-20Alkylaryl group, C_7-20Aralkyl or C_6-20Aryl radicals, especially C_1-10Alkyl radical, C_6-10Aryl or C_7-12Aralkyl radicals, e.g. C_1-8An alkyl group. Most particularly preferred hydrocarbyl groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C_5-6-cycloalkyl, cyclohexylmethyl, phenyl or benzyl.

When referring to a complex definition, the term "halo" includes fluoro, chloro, bromo and iodo groups, especially chloro or fluoro groups.

The oxidation state of the metal ions is mainly determined by the nature of the metal ions in question and the stability of the individual oxidation states of each metal ion.

It will be appreciated that in the complexes of the invention, the metal ion is coordinated by the ligand X to satisfy the valency of the metal ion and to fill its available coordination sites. The nature of these sigma-ligands can vary widely.

The numbering of these rings is evident from the structure herein.

In this application, catalyst activity is defined as the amount of polymer produced per gram of catalyst per hour. In this application, catalyst metal activity is defined as the amount of polymer produced per gram of metal per hour. The term productivity is also sometimes used to refer to catalyst activity, although in this context it refers to the amount of polymer produced per unit weight of catalyst.

The term "molecular weight" as used herein, unless otherwise indicated, refers to the weight average molecular weight Mw.

The amount of Crystalline Fraction (CF) and the amount of Soluble Fraction (SF) were determined in 1,2, 4-trichlorobenzene at 40 ℃. The crystalline fraction is the fraction of the heterophasic propylene ethylene or 1-butene copolymer that is insoluble in the solvent. The soluble fraction is correspondingly the dissolved fraction.

Detailed description of the invention

The present invention relates to a series of metallocene complexes and catalysts, which are ideal candidates for the production of heterophasic polypropylenes, in which the rubber phase (or soluble fraction) has a high molecular weight, exhibiting a high intrinsic viscosity. The matrix phase (or crystalline fraction) and thus the heterophasic polypropylene itself may have a high melting point. The metallocene complexes of the present invention are asymmetric. Asymmetric means that the two pi-ligands forming the metallocene are different.

The metallocene complexes of the invention are preferably chiral, racemic bridged bis-indenyl C in their trans-configuration₁-a symmetric metallocene. Although the complex of the present invention is formally C₁Symmetrical, but the complex ideally remains pseudo-C₂Symmetry since they maintain C near the metal center₂Symmetry, although not at the ligand periphery. In terms of their chemical nature, the antipodal and cis-enantiomeric pairs (at C) are formed during the synthesis of the complexes₁In the case of symmetric complexes). For the purposes of the present invention, rac-trans means that the two indenyl ligands are oriented in opposite directions relative to the plane of the cyclopentadienyl-metal-cyclopentadienyl, while rac-cis means that the two indenyl ligands are oriented in the same direction relative to the plane of the cyclopentadienyl-metal-cyclopentadienyl, as shown below.

Formula (I), formula 5, formula 1a, and any subformulae are intended to encompass the cis and trans configurations. Preferred metallocene catalyst complexes are in the trans configuration.

The metallocene complexes of the invention are preferably used as the rac-trans isomer. Ideally, therefore, at least 95 mole%, such as at least 98 mole%, especially at least 99 mole% of the metallocene catalyst complex is in the rac-trans isomer form.

Metallocene complexes

The metallocene complex of the invention is represented by the formula (I):

in the complex of formula (I), each X is a sigma-ligand. Most preferably, each X is independently a hydrogen atom, a halogen atom, C_1-6Alkoxy orR 'group, wherein R' is C_1-6Alkyl, phenyl or benzyl. Most preferably, X is chloro, benzyl or methyl. Preferably, both X groups are the same. The most preferred choices are two chlorides, two methyl groups or two benzyl groups, especially two chlorides.

At the bridge group R₂In Si-, at least one R is methyl or ethyl and the other R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl, pentyl, hexyl, cyclohexyl and phenyl.

Preferably, of the formula R₂Si-represents Me₂Si-，Et₂Si-or (cyclohexyl) Me-Si-. The most preferred bridge is-Si (CH)₃)₂Or Et₂Si-。

Each R¹Independently are the same or may be different and are CH₂-R⁷Group, wherein R⁷Is H or straight or branched C_1-6Alkyl radicals, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, C_3-8Cycloalkyl (e.g. cyclohexyl) or C_6-10Aryl (preferably phenyl).

Preferably, two R¹The radicals are the same and are CH₂-R⁷Group, wherein R⁷Is H or straight or branched C_1-4Alkyl, more preferably, two R ¹The radicals are the same and are CH₂-R⁷Group, wherein R⁷Is H or straight or branched C_1-3An alkyl group. Most preferably, two R¹The radicals are all methyl.

Each R²Independently is-CH ═, -CY ═ CH₂-, -CHY-or-CY₂A radical in which Y is C_1-10Hydrocarbyl, preferably C_1-4A hydrocarbyl group and wherein n is 2 to 6, preferably 3 to 4. Ideally, R²Together with the atoms of the benzene ring, form a five-membered ring. Preferably R²is-CH₂-and n is 3.

Each substituent R³And R⁴Independently are the same or can be different and are hydrogen, straight-chain or branched C_1-6Alkyl radical, C_7-20Aralkyl radical, C_7-20Alkylaryl group, C_6-20Aryl or-OY radicals, in which Y is C_1-6A hydrocarbyl group; any of the following needs is satisfied:

(A) at least one R per phenyl group³And at least one R⁴Is not hydrogen, and wherein at least one R is per phenyl group³And at least one R⁴Is hydrogen; or

(B) A R³Is an-OY group wherein Y is C_1-6A hydrocarbon radical, in the 4-position of each phenyl radical, the other two R³The group is tert-butyl; and/or

(C) A R⁴Is an-OY group wherein Y is C_1-6A hydrocarbon radical, in the 4-position of the phenyl ring, two further R⁴The group is tert-butyl.

The phenyl ring may be mono-, di-or tri-substituted.

More preferably, R³And R⁴Is hydrogen or straight or branched C_1-4Alkyl or-OY radicals in which Y is C_1-4A hydrocarbyl group. Even more preferably, each R ³And R⁴Independently hydrogen, methyl, ethyl, isopropyl, tert-butyl or methoxy, especially hydrogen, methyl or tert-butyl, wherein at least one R per phenyl group³And at least one R⁴Is not hydrogen and wherein each phenyl group has at least one R³And at least one R⁴Is hydrogen; or

At least one R³Is a methoxy group in the 4-position of each phenyl group, the other two R groups³The group is tert-butyl; and/or

At least one R⁴Is methoxy at the 4-position of the benzene ring, and the other two R⁴Is a tert-butyl group.

Thus, in one embodiment, one or two R per phenyl group³Not hydrogen, but one or two R³The radical is hydrogen.

If there are two non-hydrogen R per phenyl group³The radical, then, represents R of hydrogen³The group is preferably in the 4-position of the ring. If there are two R's representing hydrogen³Radical, then not hydrogen R³The radical is preferably present in the 4-position of the ring.

Most preferably two R³The groups are the same. For all quilt R³Two phenyl groups substituted by radicals, preferred knotsThe structure is 3',5' -dimethyl or 4' -tert-butyl. Alternatively, the structure is 3, 5-di-tert-butyl-4-methoxyphenyl.

For indenyl moieties, in one embodiment, one or two R on the phenyl group⁴The radical is not hydrogen. More preferably, two R⁴The radical is not hydrogen. If there are two non-hydrogen R ⁴Group, then represents R of hydrogen⁴Preferably in the 4-position of the ring. If there are two R's representing hydrogen⁴Radical, then not hydrogen R⁴The group is preferably present at the 4-position of the ring.

Most preferably two R⁴Likewise, for example, 3',5' -dimethyl or 3',5' -di-tert-butyl. Another option is 3',5' -di-tert-butyl-4-methoxyphenyl.

R⁵Is straight or branched C_1-6Alkyl radicals, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, C_7-20Aralkyl radical, C_7-20Alkylaryl or C_6-20And (4) an aryl group. R⁵Preferably straight or branched C_1-6Alkyl or C_6-20Aryl, more preferably straight chain C_1-4Alkyl, even more preferably C₁Or C₂Alkyl, most preferably methyl.

preferably each R⁸Identical or different, R⁸Is straight or branched C_1-4Alkyl, more preferably R⁸Are the same and are C₁Or C₂An alkyl group. Most preferably, all R⁸The radicals are all methyl.

In a preferred embodiment, the present invention provides a metallocene complex represented by the formula (II)

Each X is selected from the group consisting of chlorine, benzyl and C_1-6Sigma-ligands for alkyl groups;

R₂si is Me₂Si or Et₂Si；

Each R³And R⁴Independently are the same or can be different and are hydrogen, straight-chain or branched C_1-6Alkyl or-OY radicals, in which Y is C_1-6A hydrocarbyl group; wherein

(A) At least one R per phenyl radical³And at least one R⁴Is not hydrogen and has at least one R per phenyl group³And at least one R⁴Is hydrogen; or

(B) At least one R³Is an-OY group wherein Y is C_1-6A hydrocarbon radical, in the 4-position of each benzene ring, two more R³The group is tert-butyl; and/or

(C) At least one R⁴Is an-OY group wherein Y is C_1-6A hydrocarbon radical, in the 4-position of the phenyl ring, two further R⁴The group is tert-butyl;

R⁵is straight or branched C_1-6An alkyl group;

R⁶is C (R)⁸)₃Group, R⁸Is straight chain or branched C₁Or C₂An alkyl group.

More preferably, the metallocene complex of the present invention is one of those represented by the formula (III)

Each X is the same and is selected from the group consisting of chlorine, benzyl and C_1-6Sigma-ligands for alkyl groups;

R₂si is Me₂Si or Et₂Si；

Each of R being other than hydrogen³Same, each non-hydrogen R⁴The same;

R³is hydrogen, straight or branched C_1-6An alkyl group;

R⁴is hydrogen, straight or branched C_1-6An alkyl group;

wherein each phenyl group has at least one R³And at least one R⁴Is not hydrogen, and wherein at least one R is per phenyl group³And at least one R⁴Is a hydrogen atom, and is,

R⁵is straight or branched C_1-4An alkyl group; and

R⁶is-C (R)⁸)₃Group, R⁸Is straight chain or branched C₁Or C₂An alkyl group.

In a further preferred embodiment, the present invention provides metallocene complexes of the formulae (IVa) to (IVd)

Wherein each X is the same and is chlorine, benzyl or C_1-6Alkyl, preferably chloro, benzyl or methyl;

each R³And R⁴Independently identical or can be different and are straight-chain or branched C_1-6An alkyl group.

Preferably, R³The groups are the same. Preferably, R⁴The groups are the same.

Particular metallocene complexes of the present invention include:

rac-trans-dimethylsilanediyl [ 2-methyl-4, 8-bis- (3',5' -dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] [ 2-methyl-4- (3',5' -dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl ] hafnium dichloride (MC-1),

rac-trans-dimethylsilanediyl [ 2-methyl-4, 8-bis- (4' -tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] [ 2-methyl-4- (3',5' -dimethyl-phenyl) -5-methoxy-6-tert-butylinden-1-yl ] hafnium dichloride (MC-2),

rac-trans-dimethylsilanediyl [ 2-methyl-4, 8-bis- (4 '-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] [ 2-methyl-4- (4' -tert-butylphenyl) -5-methoxy-6-tert-butylinden-1-yl ] hafnium dichloride (MC-3),

rac-trans-dimethylsilanediyl [ 2-methyl-4, 8-bis- (3',5' -dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] [ 2-methyl-4- (3',5' -di-tert-butyl-phenyl) -5-methoxy-6-tert-butylinden-1-yl ] hafnium dichloride (MC-4),

Rac-trans-dimethylsilanediyl [ 2-methyl-4, 8-bis- (3',5' -dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] [ 2-methyl-4- (4' -tert-butylphenyl) -5-methoxy-6-tert-butylinden-1-yl ] hafnium dichloride (MC-5),

or its corresponding dimethyl analog.

For the avoidance of doubt, any of the narrow definitions of substituents provided above may be combined with any other broad or narrow definition of any other substituent.

In the above disclosure, when a narrow definition of a substituent is given, the narrow definition is considered to be disclosed together with all broad and narrow definitions of other substituents in the present application.

Synthesis of

The ligands required to form the catalysts of the invention can be synthesized by any method, and the skilled organic chemist will be able to design various synthetic schemes for making the necessary ligand materials. WO2007/116034 discloses the chemical composition of the essential materials and is incorporated herein by reference. Synthetic schemes can also be generally found in WO2002/02576, WO2011/135004, WO2012/084961, WO2012/001052, WO2011/076780, WO2015/158790 and WO 2019/179959, wherein the scheme in WO 2019/179959 shown below is most relevant to the present invention. The examples section also provides the skilled person with adequate guidance.

Containing two (R) in the formula (I)³)₃-synthesis of ligands of metallocene complexes of phenyl substituents, preferably of indacenyl ligands.

Ligands for metallocenes as disclosed in WO2018/122134 comprise two different indenes, one methoxyindene and one indene. The synthesis of methoxyindene is simple and high in yield, whereas the synthesis of asymmetric indacene requires several steps, as shown in scheme 1 for 4- (4-tert-butylphenyl) indene:

comprising two (R)³)₃-ligands of metallocene catalyst complexes of formula (I) substituted by phenyl groups, preferably asymmetric indacene ligands for the synthesis of the metallocene complexes of the invention, whose structure is similar to that described above, can be obtained in a few steps, as shown in scheme 2:

the novel ligands of the metallocene catalyst complexes of the invention can therefore be prepared in a simpler manner and, as shown in the experimental part, also in a more efficient manner. Such a process may require the following steps:

1) starting ketone compounds, e.g. R¹-3,5,6, 7-tetrahydro-s-indacen-1 (2H) -one electrophilicated with dibromo

2) From the corresponding dibromo compounds obtained in step 1, e.g. 4, 8-dibromo-R¹-3,5,6, 7-tetrahydro-s-indacen-1 (2H) -one, reduced and then methylated to give the corresponding OMe-compound

3) The corresponding OMe-compound obtained from step 2 and (R)³)₃-phenylmagnesium bromide Kumada coupling and

4) demethoxylation of the compound of step 3.

Further steps of the metallocene complexes of the formula I can be prepared according to the methods described below. The process is also applicable to a wider range of metallocenes, as described below. It will be appreciated that the metallocene obtained may exist as a trans isomer or a cis isomer. Preferably, however, the metallocenes of the present invention are trans isomers. The present invention therefore also relates to a process for isomerizing a mixture of trans and cis isomers to increase the trans isomer content of the mixture.

The metallocene with a bridged, substituted bisindenyl ligand may be C₂-symmetry or C₁Symmetrical, the latter maintaining a pseudo-C in the vicinity of the metal₂And (4) symmetry. According to the normal synthetic procedure, the synthesis procedure is carried out,C₂-a symmetric chiral metallocene and a chiral C₁Symmetrical metallocenes are generally obtained in a ratio close to 1:1, in the form of their achiral (meso) isomer or of a mixture of cis isomers. This means that about half of the final metallocene product must be discarded, resulting in a product loss of at least 50%. Furthermore, C₂Desired racemates or C of symmetrical metallocenes ₁Purification of the anti-racemic isomer of the symmetric metallocene requires several extraction-crystallization steps, further reducing the yield of the desired isomer.

Thus, according to another aspect, the invention relates to an alternative synthesis in which a combination of trans/cis-ligands undergoes epimerisation, thereby increasing the desired C₁Isolated yields of trans isomers of symmetrical metallocenes.

The substitutional synthesis for increasing the trans isomer content in the mixture of trans and cis isomers of metallocene complexes is applicable to metallocene complexes according to formulas 1a and subformulae as defined below and comprises the use of at least one compound selected from the group consisting of R^y ₄NBr，R^y ₄A step of treating said mixture with an epimerization agent of the group consisting of NCl and LiCl, wherein each R^yIndependently selected from C₁-C₂₀A group consisting of hydrocarbon groups.

If the epimerising agent is selected from the group consisting of R^y ₄NBr and R^y ₄Group of NCl, wherein R^yIndependently selected from C₁-C₂₀The treatment is preferably carried out in the presence of a liquid phase comprising or essentially consisting of at least one non-aromatic chlorinated compound (aa), or at least one non-cyclic ether compound (bb), more preferably embodiment (aa).

In this context, the phrase "consisting essentially of" denotes a composition comprising more than 90wt. -%, more preferably more than 95wt. -%, even more preferably more than 98wt. -%, in particular more than 99wt. -% of the corresponding compound.

Specific examples of the non-aromatic chlorinated compound (aa) are chloroform, dichloromethane, ethyl chloride, tetrachloroethane and the like, and chloroform, ethyl chloride and dichloromethane are particularly preferable. The latter compounds are particularly preferred because they are polar and low boiling.

The treatment of said mixture in the liquid phase according to (aa) is preferably carried out at a temperature below 80 ℃, more preferably below 65 ℃, even more preferably below 50 ℃, for example at a temperature between-30 ℃ and 50 ℃. In this case, it is most preferable if at least one selected from the group consisting of R is used^y ₄NBr、R^y ₄Treating a mixture of trans-and cis-isomers of a metallocene complex according to the following formula 1a in a liquid phase consisting essentially of at least one non-aromatic chlorinated compound (aa) at a temperature between 0 ℃ and 50 ℃.

A specific example of the acyclic ether compound (bb) is dibutyl ether. If at least one member selected from the group consisting of R is used in the liquid phase according to (bb)^y ₄NBr，R^y ₄The epimerization agent of the group consisting of NCl treats the mixture of trans-and cis-isomers of the metallocene complex according to the following formula 1a at a temperature which is preferably set to a temperature above 100 ℃, more preferably in the range of 100 ℃ to 150 ℃, even more preferably in the range of 100 ℃ to 140 ℃, in particular in the range of 110 ° to 130 ℃.

Alternatively, if the epimerising agent is LiCl, the treatment of the mixture of trans-and cis-isomers of the metallocene complex according to formula 1a is preferably carried out in a liquid phase comprising or essentially consisting of an ether, in particular Tetrahydrofuran (THF). Also in this context, the phrase "consisting essentially of" denotes a composition comprising more than 90wt. -% of the respective compound, more preferably more than 95wt. -%, even more preferably more than 98wt. -%, in particular more than 99wt. -%.

If LiCl is used as epimerising agent, the temperature is preferably maintained in the range of 40 ℃ to 90 ℃ during the treatment. Even more preferred temperature range is 55 ℃ to 85 ℃. In a preferred embodiment of the synthesis for increasing the trans isomer content, LiCl and a cyclic ether, such as THF, are added to a mixture of trans and cis isomers of the metallocene complex according to formula 1 a.

In all embodiments of the above synthesis, the mixture of trans-and cis-isomers of the metallocene complex according to formula 1a is preferably subjected to at least 1 hour, more preferably at least 5 hours, even preferably at least 15 hours, in particular at least 40 hours.

In a preferred embodiment, the epimerization agent is selected from the group consisting of R ^y ₄NBr，R^y ₄NCl and LiCl, wherein R^yIs independently selected from C₁-C₁₀A hydrocarbyl group. Further preferred is R^yIndependently selected from C₁-C₈A hydrocarbyl group. It is particularly advantageous if the epimerization agent is triethylbenzylammonium chloride (TEBAC) or LiCl.

Metallocenes suitable for the above synthesis are metallocenes of formula 1a, 2a, 3a, 4a or of formulae 5 to 8 as described below.

In the metallocene complex of the following formula 1a

Mt is Zr or Hf;

each X is a sigma-ligand;

n is 1 or 2;

l is C, Si or Ge, and

two R¹The radicals, which may be identical or different, are hydrogen or C_1-20Hydrocarbyl optionally containing up to 2 silicon or other heteroatoms, preferably C_1-8Hydrocarbyl, most preferably one R¹Is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, cyclopentyl, hexyl, octyl, the other R¹Selected from methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, trimethylsilyl, phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, biphenyl, p-trimethylsilylphenyl, p-triethylsilyl, or

LR¹ ₂The group is 9-silafluorenyl;

R²and R^2’Independently of one another are hydrogen, OSiR₃(wherein each R is independently C_1-10Hydrocarbyl) or C_1-22Hydrocarbyl, preferably CH₂-R^xRadicals or CH-R^x ₂，R^xIs hydrogen or straight or branched C_1-6Alkyl radical, C_3-8Cycloalkyl or C_6-10An aryl group;

R⁴，R⁵，R⁶，R^4’，R^5’，R^6’independently the same or may be different and is hydrogen or a hydrocarbyl group, optionally containing heteroatoms or Si atoms;

R⁷is C₂-C₂₂A hydrocarbyl group, optionally containing one or two silicon atoms or one or more heteroatoms selected from O, N, S, P and combinations thereof;

R^7’is hydrogen or C_1-3Alkyl or OCH₃A group; and

optionally, two adjacent R⁴、R⁵、R⁶、R⁷、R^4’、R^5’、R^6’、R^7’The group may be part of an aromatic or heteroaromatic ring, including the indenyl carbons to which they are bonded.

Ideally, two adjacent R⁴、R⁵、R⁶、R⁷、R^4’、R^5’、R^6’、R^7’The groups form a heteroaromatic 4 to 8 membered ring, including the indenyl carbons to which they are bonded.

In the metallocene complex of the following formula 2a

Mt is Zr or Hf;

n is 1;

each X is a sigma-ligand;

l is C, Si or Ge, and

two R¹A group, canIdentical or different, is hydrogen or C_1-20Hydrocarbyl optionally containing up to 2 silicon or other heteroatoms, preferably C_1-8Hydrocarbyl, most preferably one R¹Is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, cyclopentyl, hexyl, octyl, another R ¹Selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, trimethylsilyl, phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, biphenyl, p-trimethylsilylphenyl, p-triethylsilyl,

or LR¹ ₂The group is 9-silafluorenyl;

ar is C₆-C₂₂Aryl, or C containing up to two heteroatoms selected from O, S, N, P and combinations thereof₃-C₂₀Heteroaryl, wherein each C, N and P are optionally substituted;

R²and R^2’Independently of one another, is straight-chain or branched C_1-22A hydrocarbyl group, optionally containing one heteroatom selected from O, S, N, P and Si;

R⁵、R⁶、R^5’、R^6’independently the same or may be different and is hydrogen or a hydrocarbyl group, optionally containing Si or other heteroatoms;

R⁷is C_3-22A hydrocarbyl group optionally containing up to two silicon atoms or up to two heteroatoms selected from O, S, N, P and combinations thereof; and

R^7’is hydrogen, C_1-3Alkyl or OCH₃A group.

It should be understood that when R is⁵、R⁶、R^5’、R^6’Containing Si or other heteroatoms, these heteroatoms may be present at any point on the substituent, e.g. R^5’An O-hydrocarbyl group may be formed.

In the metallocene complex of the following formula 3a

Mt is Zr or Hf;

two R¹The radicals, which may be identical or different, are hydrogen or C_1-20Hydrocarbyl, optionally containing up to 2 silicon or other heteroatoms, preferably C_1-8Hydrocarbyl, most preferably one R¹Is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, cyclopentyl, hexyl, octyl, another R¹Selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, trimethylsilyl, phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, biphenyl, p-trimethylsilylphenyl, p-triethylsilyl,

or R¹ ₂Si is 9-silafluorenyl;

ar is independently of each other phenyl or substituted phenyl, naphthyl or substituted naphthyl, anthracenyl, pyridinyl, thienyl, 5-alkylthiophen-2-yl, benzothienyl, pyrrolyl, furanyl, 5-alkylfuran-2-yl;

R⁵、R⁶independently of one another, hydrogen or a hydrocarbon radical; and optionally, R ⁵，R⁶The group may be part of a 4 to 8 membered aromatic ring, including the indenyl carbons to which they are bonded;

R⁵' is hydrogen, a hydrocarbon group or an OY group, wherein Y is C_1-10A hydrocarbyl group;

R⁶' is of the formula CH-R^x ₂A secondary hydrocarbon radical of the formula CR^x ₃In which R is a tertiary hydrocarbon group of^xIs straight or branched C_1-6Alkyl, aryl, heteroaryl, and heteroaryl,C_3-8Cycloalkyl radical, C_6-10An aryl group; and optionally, R^5’、R^6’The group may be part of a 4 to 7 membered aromatic ring including the indenyl carbons to which they are bonded.

In a preferred embodiment, if R in formula 3a is⁶' is a tertiary hydrocarbon group, then R⁵' is hydrogen.

In the metallocene complex of the following formula 4a

Mt is Zr or Hf;

two R¹The radicals being, independently of one another, hydrogen or C_1-20Hydrocarbyl optionally containing up to 2 silicon or other heteroatoms, preferably C_1-8Hydrocarbyl, most preferably one R¹Is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, cyclopentyl, hexyl, octyl, a second R¹Selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, trimethylsilyl, phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, biphenyl, p-trimethylsilylphenyl, p-triethylsilyl,

Or R¹ ₂Si is 9-silafluorenyl;

R²and R^2’Independently of one another, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutyl, pentyl, hexyl, C_6-10Aryl or thiophenyl, 5-alkylthiophen-2-yl, pyrrolyl, furanyl, 5-alkylfuran-2-yl;

R⁵and R⁶Independently of one another are hydrogen or C_1-20Hydrocarbyl optionally containing up to 2 silicon or heteroatoms, or-CH ═ CY ═ CH₂-, -CHY-or-CY₂-groups which are part of a cyclic structure of 4 to 7 atoms, including the indenyl carbons to which they are bound;

R^5’is C_1-6A hydrocarbyl or OY group;

R⁶' is formula CR^x ₃In which R is a tertiary hydrocarbon group of^xIs straight or branched C_1-6Alkyl radical, C_3-8Cycloalkyl radical, C_6-10An aryl group;

each R⁸And R⁹Independently are the same or can be different and are hydrogen, straight-chain or branched C₁-C₆Alkyl, OY radical, C₇-₂₀Aralkyl radical, C_7-20Alkylaryl or C_6-20Aryl, and optionally two adjacent R⁸Or R⁹The groups may be part of a ring, including the phenyl carbons to which they are bonded;

wherein at each occurrence Y is C_1-10A hydrocarbyl group.

The alternative synthesis as described above allows to produce a mixture having a ratio of trans and cis isomers of at least 90:10, preferably at least 95:5, more preferably at least 97:3, when starting from a rich-trans mixture having a ratio of trans to cis isomers of at least 65: 35. No subsequent purification is required. Pure trans isomers can be obtained by a single crystallization or solvent extraction step. Other metallocenes suitable for use in this alternative synthesis process of the present invention are bridged asymmetric bis indenyl metallocenes in racemic configuration having the structure described by formula 5:

Wherein Mt is Zr or Hf;

each X is a sigma-ligand;

the two R groups, which may be identical or different, are C_1-20Hydrocarbyl, optionally containing up to 2 silicon or hetero atoms, preferably C_1-8A hydrocarbyl group; most preferably one R is methyl, ethyl, n-propyl or isopropyl and the other R is selected from methyl, ethyl, n-propyl, isopropyl,N-butyl, isobutyl, pentyl, hexyl, cyclohexyl and phenyl;

R¹and R^1’The same or may be different;

R¹is CH₂-R²Group, R²Is H or straight or branched C_1-6Alkyl radical, C_3-8Cycloalkyl radical, C_6-10An aryl group;

R^1’is C_1-20A hydrocarbyl group; preferably, R¹And R^1’Identical and are straight-chain or branched C_1-6An alkyl group;

each R⁵And R⁶Independently is hydrogen or C_1-20Hydrocarbyl optionally containing up to 2 silicon or heteroatoms and preferably together forming-CH ═ CY ═ CH₂-, -CHY-or-CY₂A group which is part of a cyclic structure of 4 to 7 atoms, comprising the carbon atoms in positions 5 and 6 of the corresponding indenyl ligand,

y is C_1-10A hydrocarbyl group;

each R³And R⁴Independently are the same or can be different and are hydrogen, straight-chain or branched C₁-C₆Alkyl, OY radicals or C₇-₂₀Aralkyl radical, C_7-20Alkylaryl or C_6-20Aryl, and optionally two adjacent R³Or R⁴The groups may be part of a ring, including the phenyl carbons to which they are bonded;

R^5’Is hydrogen or straight, branched or cyclic C₁-C₆Alkyl radical, C_7-20Aralkyl, C_7-20Alkylaryl or C₆-C₂₀Aryl, or OY groups;

R^6’is hydrogen or straight, branched or cyclic C₁-C₆Alkyl radical, C_7-20Aralkyl radical, C_7-20Alkylaryl or C₆-C₂₀Aryl, or OY groups;

with the proviso that when R^5’When it is an-OY group, R^6’is-C (R)⁸)₃Group, wherein R⁸Is straight chain or branched C₁-C₆An alkyl group;

R⁷is C optionally containing up to two silicon or hetero atoms_1-20A hydrocarbon radical or a radical of 3,4, 5-three R³-a phenyl group;

R^7’is hydrogen or C_1-3A hydrocarbyl or OY group;

and with the proviso that only when R^7’When different from hydrogen, R^6’Can be hydrogen.

Preferably, the metallocene suitable for use in the synthesis process of the present invention is a bridged asymmetric bis indenyl metallocene of racemic configuration having the structure shown in formula 6:

wherein Mt, X, R¹、R^1’、R³、R⁴、R⁵、R^5’、R⁶、R^6’And R^7’As described above.

Most preferably, the metallocene suitable for use in the synthesis process of the present invention is a bridged asymmetric bis indenyl metallocene of racemic configuration having the structure described by formula 7:

wherein Mt, X, R, R¹、R^1’、R³、R⁴、R⁵、R^5’、R⁶And R^6’As described above.

Most preferably, the metallocene suitable for use in the synthesis process of the present invention is a bridged asymmetric bis indenyl metallocene of racemic configuration having the structure described by formula 8:

x, R, R therein¹、R^1’、R³、R⁴、R⁵、R^5’、R⁶And R^6”As described in formula 5 above, and each R ²Independently is-CH ═ CY ═ CH₂-, -CHY-or-CY₂-a group wherein Y is C_1-6A hydrocarbyl group and wherein n is 2 to 6. In formula 8, R⁵Especially C_1-10A hydrocarbyl group.

The preferred options for substituents described above also apply to formulae 5 to 7.

Thus, the metallocenes of formula I of the present invention may be synthesized according to the alternative methods described herein.

Typically, the isomerization is carried out at one or more temperatures in the range of from room temperature to 200 ℃, preferably in the range of from 0 to 150 ℃, more preferably in the range of from room temperature to 80 ℃. The rate of isomerization varies with temperature and is therefore generally faster at higher temperatures and slower at lower temperatures. Thus, the isomerization reaction is conducted for a sufficient period of time and under conditions to achieve the appropriate or desired amount of isomerization. Typically the isomerization time is in the range of 0.5 to 96 hours. For isomerization temperatures in the range of room temperature to 80 ℃, a time period in the range of 1 to 48 hours is preferred. One skilled in the art can find suitable combinations of time and temperature for epimerization. It is desirable to stir the isomerization mixture during at least a substantial portion of the isomerization reaction.

However, it should be noted that the rate of isomerization also varies with the type of liquid phase used. During synthesis, the liquid phase suitable for use as an isomerization medium comprises or consists essentially of polar aprotic organic compounds, such as ethers, tertiary amines, and/or non-aromatic chlorinated compounds.

The ethers used to form the isomerization medium preferably include cyclic and acyclic monoethers and polyethers that exist as liquids at, preferably below, the lowest isomerization temperature used in carrying out a particular isomerization operation. However, ethers which are present in the solid state at the lowest isomerization temperature used may be used, provided that these ethers are used in admixture with further inert liquid solvents, such as liquid hydrocarbons or liquid tertiary amines, in which the ether is soluble at the lowest isomerization temperature, thereby providing a continuous liquid phase in which the isomerization is to be carried out.

Typical ethers that may be used include acyclic ethers such as dialkyl ethers, dicycloalkyl ethers, diaralkyl ethers, diaryl ethers, alkyl-aryl ethers, and alkyl-cycloalkyl ethers; dialkyl ethers of glycols such as those of ethylene glycol, propylene glycol, 1, 4-butanediol, etc.; trialkyl ethers of triols, such as trialkyl ethers of glycerol, dialkyl ethers of diethylene glycol; dialkyl ethers of triethylene glycol; dialkyl ethers of tetraethylene glycol; and similar liquid acyclic ethers. Preferred for forming the isomerization medium are cyclic ethers and polyethers having at least 5-membered rings, such as tetrahydrofuran, 2, 3-benzofuran, alkyldihydrofuran, alkyltetrahydrofuran, alkyltetrahydrofurfuryl ether, alkyldihydropyran, tetrahydropyran, 1, 4-dioxane, 1, 3-dioxolane and similar liquid cyclic ethers. When another type of inert solvent (e.g., an inert liquid hydrocarbon solvent, a liquid tertiary amine, a liquid mixture of hydrocarbons and tertiary amines, etc.) is used in combination with one or more ethers to form the isomerization medium, the resulting liquid medium preferably contains at least 70 volume percent, more preferably at least 80 volume percent, and most preferably at least 90 volume percent ether.

The ratio between the ether-containing liquid phase and the mixture of cis-metallocene and trans-metallocene must be such that a fine solution is formed, but also a slurry is formed, wherein a portion of the metallocene is in solution and a portion of the metallocene is in the form of solid particles in a continuous liquid phase. For efficient operation, the proportions used are generally such as to provide a solution or slurry in which the mixture comprises solid particles in an amount in the range of from 0 to 95% by weight.

The manner in which the initial mixture of cis-metallocene and trans-metallocene isomers is produced or formed is not critical. It is important that the initial mixture can be treated in accordance with the present invention so that the trans isomer content of the mixture can be increased by practicing the present invention.

Thus viewed from a further aspect the invention provides a method of increasing the trans isomer content of a mixture of trans-metallocene and cis-metallocene isomers, for example those of formulae 1a to 4a or formulae 5 to 8 as defined above;

wherein the process comprises adding the mixture to a liquid phase comprising at least one ether compound or at least one non-aromatic chlorinated compound at a temperature of from 0 to 200 ℃, preferably from 0 to 150 ℃, more preferably from 20 to 80 ℃, forming a solution or slurry of the mixture in the liquid phase, wherein a portion of the mixture is in the form of solid particles in the liquid phase and a portion of the mixture is dissolved in the ether or non-aromatic chlorinated compound;

And the trans-isomer content of the mixture is increased by epimerization in said liquid phase.

In particular, the invention relates to the addition of racemic trans-isomer from a mixture of racemic trans-and cis-isomers.

Viewed from another aspect, the invention provides a method of increasing C₁-a method of trans isomer content in symmetrical trans and cis biscyclopentadienyl metallocene isomer mixtures, such as those of formulae 1a to 4a or formulae 5 to 8 as defined above;

wherein the process comprises adding the mixture to a liquid phase comprising at least one ether compound or at least one non-aromatic chlorinated compound at a temperature of from 0 to 200 ℃, preferably from 0 to 150 ℃, more preferably from 20 to 80 ℃, to form a solution or slurry of the mixture in the liquid phase, wherein a portion of the mixture is in the form of solid particles in the liquid phase and a portion of the mixture is dissolved in the ether or non-aromatic chlorinated compound;

and the trans-isomer content of the mixture is increased by isomerization in said liquid phase.

Co-catalyst

In order to form the active catalytic species, it is generally necessary to use a cocatalyst as is well known in the art.

According to the present invention a cocatalyst system comprising a boron-containing cocatalyst and/or an aluminoxane cocatalyst is used in combination with the metallocene catalyst complex defined above.

The aluminoxane cocatalyst can be any of the compounds represented by the formula (X):

wherein n is typically 6 to 20 and R has the following meaning.

Aluminoxanes are formed on partial hydrolysis of an organoaluminum compound, for example of the formula AlR₃、AlR₂Y and Al₂R₃Y₃Wherein R may be, for example, C₁-C₁₀Alkyl, preferably C₁-C₅Alkyl, or C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl or alkylaryl and/or phenyl or naphthyl, and wherein Y can be hydrogen, halogen, preferably chlorine or bromine, or C₁-C₁₀-alkoxy, preferably methoxy or ethoxy. The resulting oxyalkanolenes are generally not pure compounds but mixtures of oligomers of the formula (X).

The preferred aluminoxane is Methylaluminoxane (MAO). Since the alumoxanes used as cocatalysts according to the present invention are not pure compounds because of their mode of preparation, the molar concentrations of the alumoxane solutions are hereinafter based on their aluminum content.

In accordance with the present invention, a boron-containing cocatalyst may also be used in place of the aluminoxane cocatalyst, or the aluminoxane cocatalyst may be used in combination with the boron-containing cocatalyst.

Those skilled in the art will appreciate that in the case of the use of a boron-based cocatalyst, the alkylation is typically pre-carried out by reacting the complex with an alkylaluminum compound, such as TIBA. This process is well known and any suitable aluminum alkyl, such as Al (C) _1-6Alkyl radical)₃May be used. Preferred alkyl aluminum compounds are triethylaluminum, triisobutylaluminum, triisohexylaluminum, tri-n-octylaluminum and triisooctylaluminum.

Alternatively, when a borate cocatalyst is used, the metallocene catalyst complex is in its alkylated form, i.e. for example a dimethyl or dibenzyl metallocene catalyst complex may be used.

Boron-containing cocatalysts of interest include those of formula (Z)

BY₃(Z)

Wherein Y is the same or different and is a hydrogen atom, an alkyl group of 1 to about 20 carbon atoms, an aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl group of 6 to about 15 carbon atoms, each having 1 to 10 carbon atoms in the alkyl group and 6 to 20 carbon atoms in the aryl group or having fluorine, chlorine, bromine or iodine. Preferred examples of Y are trifluoromethyl, unsaturated groups such as haloaryl groups, e.g. p-fluorophenyl, 3, 5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4, 5-trifluorophenyl and 3, 5-bis (trifluoromethyl) phenyl. Preferred choices are trifluoroborane, tris (4-fluorophenyl) borane, tris (3, 5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (2,4, 6-trifluorophenyl) borane, tris (pentafluorophenyl) borane, tris (3, 5-difluorophenyl) borane and/or tris (3,4, 5-trifluorophenyl) borane.

Particular preference is given to tris (pentafluorophenyl) borane.

However, it is preferred to use borates, i.e. compounds containing borate anions. Such ionic cocatalysts preferably contain a non-coordinating anion, such as tetrakis (pentafluorophenyl) borate. Suitable counterions are protonated amine or aniline derivatives, for example methylammonium, anilinium, dimethylammonium, diethylammonium, N-methylanilinium, diphenylammonium, N-dimethylanilinium, trimethylammonium, triethylammonium, tri-N-butylammonium, methyldiphenylammonium, pyridine (pyridinium), p-bromo-N, N-dimethylanilinium or p-nitro-N, N-dimethylanilinium.

Preferred ionic compounds that may be used according to the present invention include: tributylammonium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (trifluoromethylphenyl) borate, tributylammonium tetrakis (4-fluorophenyl) borate, N, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylbenzylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-di (propyl) ammonium tetrakis (pentafluorophenyl) borate, di (cyclohexyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, triethylphosphonium tetrakis (pentafluorophenyl) borate, diphenylphosphonium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, or ferrocenium tetrakis (pentafluorophenyl) borate.

Preference is given to triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate and N, N-dimethylbenzylammonium tetrakis (pentafluorophenyl) borate.

Particular preference is given to triphenylcarbenium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

Therefore, it is particularly preferable to use Ph₃CB(PhF₅)₄And the like.

Preferred cocatalysts according to the present invention are aluminoxanes, more preferably methylaluminoxane, combinations of aluminoxane with aluminum alkyl, boron or borate cocatalysts and combinations of aluminoxane with boron based cocatalysts.

According to the most preferred embodiment of the present invention, the preferred cocatalyst is an aluminoxane, most preferably methylaluminoxane with a borate cocatalyst such as N, N-dimethylammonium-tetrakispentafluorophenylborate and Ph₃CB(PhF₅)₄Combinations of (a) and (b). Particularly preferred is a combination of methylalumoxane and trityl borate.

Suitable amounts of co-catalyst are well known to the skilled person.

The molar ratio of the boron feed to the metal ions of the metallocene may be in the range from 0.1:1 to 10:1mol/mol, preferably from 0.3:1 to 7:1, especially from 0.3:1 to 5:1 mol/mol.

The molar ratio of Al in the aluminoxane to the metal ion of the metallocene may be in the range of from 1:1 to 2000:1mol/mol, preferably from 10:1 to 1000:1, more preferably from 50:1 to 500:1 mol/mol.

The catalyst may contain from 10 to 100. mu. mol of metallocene metal ions and from 5 to 10mmol of Al per gram of silica.

Catalyst production

The metallocene catalyst complexes of the present invention may be used in combination with a suitable cocatalyst as catalysts for the polymerization of propylene, for example in solvents such as toluene or aliphatic hydrocarbons (i.e. for polymerization in solution), as is well known in the art.

The catalysts of the invention can be used in supported or unsupported form. Preferably, the catalyst system of the present invention is used in supported form. The particulate support materials used are preferably organic or inorganic materials, for example silica, alumina or zirconia or mixed oxides, for example silica-alumina, in particular silica, alumina or silica-alumina. Preferably, a silica support is used. The skilled person is aware of the procedures required to support the metallocene catalyst. It is particularly preferred that the support is a porous material such that the complex can be loaded into the pores of the support, for example using a method similar to that described in WO94/14856, WO95/12622 and WO 2006/097497.

The average particle size of the silica support may typically be from 10 to 100 μm. However, it has turned out that particular advantages can be achieved if the support has an average particle diameter of from 15 to 80 μm, preferably from 18 to 50 μm.

The silica support may have an average pore diameter in the range of 10 to 100nm and a pore volume of between 1 and 3 mL/g.

Examples of suitable support materials are, for example, ES757 manufactured and sold by PQ Corporation, Sylopol 948 manufactured and sold by Grace, or SUNSPERA DM-L-303 silica manufactured by AGC Si-Tech Co.

The support may optionally be calcined prior to use in catalyst preparation to achieve an optimum silanol group content.

The use of such carriers is conventional in the art.

In an alternative embodiment, no carrier is used at all. Such catalysts may be prepared in solution, for example in an aromatic solvent such as toluene, by contacting the metallocene (as a solid or as a solution) with a cocatalyst, for example methylaluminoxane or borane or a borate previously dissolved in an aromatic solvent, or by adding the dissolved catalyst components sequentially to the polymerization medium.

In one embodiment, no external support is used, but the catalyst is still present in the form of solid particles. Thus, instead of using an external support material, such as an inert organic or inorganic support, for example silica as described above, an emulsion-curing process is used to prepare the solid catalyst. The entire disclosure of the process is described in WO2003/051934, which is incorporated herein by reference.

In one embodiment, the preparation of the catalyst system according to the invention comprises the following steps:

a') reacting the silica support with the aluminoxane cocatalyst in a suitable hydrocarbon solvent, such as toluene, and optionally followed by washing and drying, to obtain a support treated with aluminoxane cocatalyst,

b') reacting the metallocene complex of formula (I) with a borate cocatalyst and optionally an aluminoxane cocatalyst, in particular methylaluminoxane, in a suitable hydrocarbon solvent such as toluene or xylene, to obtain a solution of the activated metallocene complex of formula (I), the borate cocatalyst and optionally the aluminoxane cocatalyst, wherein the borate cocatalyst is added in such an amount that the boron/hafnium molar ratio of the feed amounts is in the range from 0.1:1 to 10:1,

c ') adding the solution obtained in step b ') to the aluminoxane cocatalyst-treated support obtained in step a '), wherein the amount of aluminoxane cocatalyst added in step a ') is from 75.0 to 100% by weight based on the total amount of aluminoxane cocatalyst, and the amount of aluminoxane cocatalyst added in step b ') is from 0 to 25.0% by weight based on the total amount of aluminoxane cocatalyst

And

d') optionally drying the supported catalyst system thus obtained.

In an alternative embodiment, the preparation of the catalyst system according to the invention comprises the following steps:

a) the silica support is reacted with the aluminoxane cocatalyst in a suitable hydrocarbon solvent, such as toluene, and optionally subjected to subsequent washing and drying, to obtain an aluminoxane cocatalyst-treated support,

b) the metallocene complex of formula (I) is reacted with an aluminoxane cocatalyst in a suitable hydrocarbon solvent such as toluene,

c) adding a borate cocatalyst to the solution obtained in step b) to obtain a solution of the metallocene complex of formula (I), borate cocatalyst and aluminoxane cocatalyst, wherein the borate cocatalyst is added in such an amount that the feeding amount of boron/hafnium reaches a molar ratio of 0.1:1 to 10:1,

d) adding the solution obtained in step c) to the aluminoxane cocatalyst treated support obtained in step a), wherein the amount of aluminoxane cocatalyst added in step a) is from 75.0% to 97.0% by weight of the total amount of aluminoxane cocatalyst and the amount of aluminoxane cocatalyst added in step b) is from 3.0% to 25.0% by weight of the total amount of aluminoxane cocatalyst;

and

e) the supported catalyst system thus obtained is optionally dried.

Polymerisation

Although the catalysts according to the invention are suitable for forming any polyolefin, for example polypropylene homo-or copolymers, they have in particular the preparation of heterophasic propylene copolymers of ethylene and optionally 1-butene.

Such polymers may be prepared in a multistage polymerization using conventional polymerization techniques, including at least two polymerization steps, such as slurry or bulk polymerization and a gas phase polymerization step. Each step may comprise one or more polymerization reactors. The polymerization in the process of the present invention may preferably be carried out in at least two or more, e.g. in 2, 3 or 4, polymerization reactors, wherein at least one reactor is a gas phase reactor. Desirably, the multistage process of the present invention uses a first reactor operating in a liquid slurry and a second and optionally a third reactor which is a gas phase reactor. The process may also employ a pre-polymerization step. The liquid slurry reaction may be carried out in a loop reactor. For the purposes of the present invention, slurry polymerization in liquid monomer is also referred to as bulk step.

In the case of propylene polymerisation for slurry reactors, the reaction temperature is typically in the range 60 to 110 ℃ (e.g. 60-90 ℃), the reactor pressure is typically in the range 5 to 80 bar (bar) (e.g. 20-60 bar), and the residence time is typically in the range 0.1 to 5 hours (e.g. 0.3 to 2 hours). Monomers are generally used as the reaction medium.

For gas phase reactors, the reaction temperature employed is typically in the range of 60 to 115 ℃ (e.g., 70 to 110 ℃), the reactor pressure is typically in the range of 10 to 25 bar (bar), and the residence time is typically 0.5 to 8 hours (e.g., 0.5 to 4 hours). The gas used will be a monomer, optionally as a mixture with a non-reactive gas such as nitrogen or propane.

The process may comprise any additional polymerization step, such as a prepolymerization step, in addition to the actual polymerization step and reactor, and any further reactor treatment step known in the art.

Generally, the amount of catalyst used will depend on the nature of the catalyst, the type of reactor and conditions, and the desired properties of the polymer product. Hydrogen may be used to control the molecular weight of the polymer, as is well known in the art.

The present invention preferably relates to the copolymerization of propylene and ethylene in at least a two-step process to form a heterophasic propylene-ethylene copolymer.

In the heterophasic propylene copolymer, the homopolymer or random copolymer matrix (M) (produced in the first step) is combined with a copolymeric amorphous fraction, i.e. an amorphous propylene-ethylene copolymer or a propylene-ethylene-1-butene copolymer (a) (formed in the second step) to form the heterophasic copolymer of the invention.

According to the present invention, an amorphous propylene-ethylene copolymer or an amorphous propylene-ethylene-1-butene copolymer (A) is formed in a gas phase reactor. In the case of a two-reactor configuration (one bulk reactor and one gas-phase reactor), the copolymer (A) is formed in the gas-phase reactor. For the purposes of the present invention, the amorphous propylene-ethylene copolymer (a) is also referred to as ethylene-propylene rubber or EPR and the amorphous propylene-ethylene-1-butene copolymer (a) is referred to as ethylene-propylene-butene rubber or EPBR.

In case two gas phase reactors are used, the first gas phase reactor may produce a homopolymer or copolymer component, ideally a homopolymer component, whereby the polymer component from such first gas phase reactor forms part of the polymer matrix (M). The propylene ethylene or propylene-ethylene-1-butene amorphous phase (a) is formed in the last gas phase step. Preferably, the amorphous phase (A) is a propylene-ethylene copolymer.

The production share may vary from reactor to reactor. When two reactors are used, the share is generally in the range from 95 to 5% by weight of bulk to gas phase to 30 to 70% by weight of bulk to gas phase. In the case of using three reactors, it is preferred that each reactor preferably produces at least 5% by weight of polymer.

The catalyst system of the present invention is particularly advantageous for use in the manufacture of heterogeneous PP/EPR reactor blends.

Viewed from this aspect, the present invention therefore provides a process for the preparation of a heterophasic polypropylene copolymer comprising:

(I) polymerizing propylene and optionally ethylene and/or 1-butene in bulk in the presence of a catalyst system as defined herein to form a polypropylene homopolymer or polypropylene random copolymer matrix;

(II) polymerising propylene and ethylene and optionally 1-butene in the gas phase in the presence of said matrix and said catalyst system to form a heterophasic polypropylene copolymer comprising a homopolymer or propylene random copolymer matrix and a propylene-ethylene rubber or a propylene-ethylene-1-butene rubber.

Viewed from another aspect the present invention provides a process for the preparation of a heterophasic polypropylene copolymer comprising:

(I) polymerizing propylene and optionally ethylene and/or 1-butene in bulk in the presence of a catalyst system as defined herein to form a polypropylene homopolymer or a propylene random copolymer;

(II) polymerising additional propylene and optionally ethylene and/or 1-butene in the gas phase in the presence of said homopolymer or propylene random copolymer and said catalyst system to form a polypropylene homopolymer matrix or a propylene random copolymer matrix;

(III) polymerising propylene and ethylene and optionally 1-butene in the gas phase in the presence of the matrix and the catalyst system to form a heterophasic polypropylene copolymer comprising a homopolymer or propylene random copolymer matrix and a propylene-ethylene rubber or propylene-ethylene-1-butene propylene rubber (EPR).

According to a preferred embodiment of the invention, the matrix is a propylene homopolymer. According to another preferred embodiment of the invention, the matrix is a random polypropylene copolymer, wherein the amount of comonomer in the matrix is up to 2 wt.%. Preferably the comonomer is ethylene.

Further, it is preferable that the propylene rubber is a propylene-ethylene rubber.

According to another aspect, the present invention comprises a process for preparing a heterophasic polypropylene copolymer comprising:

(I) polymerizing propylene and optionally ethylene and/or 1-butene in a first step, comprising a bulk phase polymerization in the presence of a catalyst, comprising:

(i) a metallocene represented by the formula (5)

Wherein Mt is Hf;

each X is a sigma-ligand;

the two R groups, which may be identical or different, are C_1-20Hydrocarbyl, optionally containing up to 2 silicon or hetero atoms, preferably C_1-8A hydrocarbyl group; most preferably one R is methyl, ethyl, n-propyl or isopropyl and the other R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, cyclohexyl and phenyl;

R¹And R^1’The same or may be different;

R¹is CH₂-R²Group, R²Is H or straight or branched C_1-6Alkyl radical, C_3-8Cycloalkyl, C_6-10An aryl group;

each R⁵And R⁶Independently is hydrogen or C_1-20Hydrocarbyl, optionally containing up to 2 silicon or heteroatoms, or together are-CH ═ CY ═ CH₂-, -CHY-or-CY₂A group which is part of a cyclic structure of 4 to 7 atoms, comprising the carbon atoms in the 5 and 6 positions of the corresponding indenyl ligand, wherein Y is C_1-10A hydrocarbyl group;

R^5’is hydrogen or straight, branched or cyclic C₁-C₆Alkyl radical, C_7-20Aralkyl radical, C_7-20Alkylaryl or C₆-C₂₀Aryl, or OY groups;

with the proviso that when R^5’When it is an OY group, R^6’Is C (R)⁸)₃Group, wherein R⁸Is straight chain or branched C₁-C₆An alkyl group;

R⁷is C optionally containing up to two silicon or hetero atoms _1-20A hydrocarbyl group;

R^7’is hydrogen or C_1-3A hydrocarbyl or OY group;

and only when R⁷' when different from hydrogen, R⁶' Only hydrogen;

(ii) a cocatalyst comprising a compound of a group 13 element;

producing a polypropylene homopolymer or propylene random copolymer matrix having a comonomer content of 2 wt% or less; subsequently in the presence of said substrate and said catalyst system;

(II) polymerizing propylene and ethylene and optionally 1-butene in the gas phase in the presence of the catalyst to form a propylene ethylene or propylene ethylene 1-butene copolymer component;

wherein the heterophasic polypropylene copolymer has an IV (SF) of 1.5 to 10dl/g, preferably 2 to 9dl/g, more preferably 4.5 to 9.0dl/g, most preferably 5.5 to 8.0dl/g,

the comonomer content, preferably the ethylene content, (SF) is from 12 to 85% by weight, preferably from 15 to 70% by weight, wherein the amount of Crystalline Fraction (CF) and the amount of Soluble Fraction (SF) are determined in 1,2, 4-trichlorobenzene at 40 ℃.

According to a preferred embodiment, the present invention comprises a process for the preparation of heterophasic polypropylene copolymers wherein the metallocene (i) has formula (6) or more preferably formula (7) as defined above.

According to another embodiment of the present invention, the first step comprises, in addition to a bulk phase polymerization step, a gas phase polymerization step as described herein.

The comonomer is preferably ethylene.

Polymer and process for producing the same

It is a feature of the present invention that the claimed catalysts are capable of forming certain heterophasic propylene copolymers. Viewed from another aspect, the present invention is capable of forming a heterophasic polypropylene copolymer having an MFR2 of from 0.05 to 100g/10min, and wherein the heterophasic polypropylene copolymer is characterized by

(a1)30.0 to 95.0 wt% of a Crystalline Fraction (CF); and

(a2)5.0 to 70.0 wt.% of a Soluble Fraction (SF) having a comonomer content, such as ethylene, of 12 to 85 wt.%, preferably 15.0 to 70.0 wt.%; and

wherein the Intrinsic Viscosity (IV) of the Soluble Fraction (SF) (in decalin at 135 ℃) is from 1.5 to 10dl/g, preferably from 2 to 9, more preferably from 4.5 to 9dl/g, most preferably from 5.5 to 8dl/g, wherein the amount of Crystalline Fraction (CF) and the amount of Soluble Fraction (SF) are determined in 1,2, 4-trichlorobenzene at 40 ℃.

Viewed from another aspect, the present invention is capable of forming a heterophasic polypropylene copolymer having an MFR2 of 0.05 to 100g/10min and a melting point (Tm) of 156 to 162 ℃ and comprising:

(a1)30.0 to 95.0% by weight of a Crystalline Fraction (CF) and

(a2)5.0 to 70.0 wt.% of a Soluble Fraction (SF) having a comonomer content, such as ethylene, of 12 to 85 wt.%, preferably 15.0 to 70.0 wt.%; and wherein the Intrinsic Viscosity (IV) of the Soluble Fraction (SF) (in decalin at 135 ℃) is from 1.5 to 10dl/g, preferably from 2 to 9dl/g, more preferably from 4.5 to 9.0dl/g, most preferably from 5.5 to 8dl/g, wherein the amount of Crystalline Fraction (CF) and the amount of Soluble Fraction (SF) are determined in 1,2, 4-trichlorobenzene at 40 ℃.

Viewed from another aspect, the invention can form a composition having an MFR2 and melting point T of 0.05 to 100g/10min_m>A heterophasic polypropylene copolymer at 158 ℃ comprising:

(a1)30.0 to 95.0% by weight of a Crystalline Fraction (CF) and

(a2)5.0 to 70.0 wt.% of a Soluble Fraction (SF) having an ethylene content of 12 to 85 wt.%, preferably 15.0 to 70.0 wt.%; and wherein the Intrinsic Viscosity (IV) (in decalin at 135 ℃) of the soluble fraction (i.e. the fraction soluble in 1,2, 4-trichlorobenzene at 40 ℃) is >5 dl/g.

By using the catalyst of the present invention, the properties of the rubber component can be tailored to achieve surprisingly high molecular weights. Furthermore, we show that the heterophasic copolymers of the present invention have a very high melting point (Tm) of 156 to 162 ℃, preferably 157 to 162 ℃, still more preferably 158 to 162 ℃.

Such heterophasic propylene copolymers (HECOs) comprise a semi-crystalline polymer matrix (M) (propylene homopolymer (hPP)) or a semi-crystalline random propylene-ethylene or propylene-ethylene-1-butene copolymer (rPP) or a combination of both, wherein the majority of the amorphous copolymer (a), such as the propylene-ethylene copolymer (EP), is dispersed (rubber phase, such as EPR).

Thus, the polypropylene matrix (M) comprises (finely) dispersed inclusions not being part of the matrix and said inclusions comprise the amorphous copolymer (a).

The term "heterophasic polypropylene copolymer" as used herein denotes a copolymer comprising a matrix resin (polypropylene homopolymer or propylene copolymer) and a predominantly amorphous copolymer (a) dispersed in the matrix resin, as defined in more detail below.

In the present invention, the term "matrix" should be interpreted in its generally accepted sense, i.e. it refers to a continuous phase (in the present invention a continuous polymer phase) in which isolated or discrete particles, such as rubber particles, may be dispersed. The propylene polymer is present in an amount such that it forms a continuous phase that can be used as a matrix.

Furthermore, the terms "amorphous copolymer", "dispersed phase", "mainly amorphous copolymer" and "rubber phase" mean the same, i.e. interchangeable in the present invention. By amorphous is meant that the copolymer has a heat of fusion of less than 20J/g when analyzed by DSC as a pure component (after extraction from the matrix by xylene extraction).

Matrix (M):

the matrix (M) of the heterophasic polypropylene copolymer is preferably a propylene homopolymer or a semi-crystalline propylene-ethylene or propylene-butene copolymer or a propylene-ethylene butene copolymer or a combination thereof. The term "semicrystalline" means that the copolymer has a well-defined melting point and a heat of fusion above 50J/g.

The expression homopolymer as used in the present invention relates to a polypropylene consisting essentially of propylene units. In a preferred embodiment, only propylene units in the propylene homopolymer are detectable.

In one embodiment, the matrix (M) comprises, preferably consists of, a propylene homopolymer as defined above or below.

The polypropylene homopolymer may comprise or consist of a single polypropylene homopolymer fraction (unimodal), but may also comprise a mixture of different polypropylene homopolymer fractions.

In case the polypropylene homopolymer comprises different fractions, the polypropylene homopolymer is understood to be bimodal or multimodal. These fractions may have different average molecular weights or different molecular weight distributions.

Preferably, the polypropylene homopolymer may be bimodal or multimodal with respect to molecular weight or molecular weight distribution.

Or, preferably, the polypropylene homopolymer may be unimodal with respect to average molecular weight and/or molecular weight distribution.

Thus, in one embodiment or the invention, the matrix (M) is unimodal, while in another embodiment the matrix (M) is bimodal and consists of two propylene homopolymer fractions (hPP-1) and (hPP-2).

In another embodiment, the matrix (M) is bimodal and consists of one homopolymer fraction and one semicrystalline copolymer fraction.

Amorphous propylene copolymer (a):

the second component of the specific heterophasic polypropylene copolymer is a propylene copolymer (a), which is an amorphous copolymer of propylene and ethylene. The second component is therefore an elastomeric copolymer, dispersed in the matrix (M) (i.e. the dispersed phase).

As mentioned above, the terms "amorphous (propylene-ethylene) copolymer", "dispersed phase" and "rubber phase" mean the same, i.e. interchangeable for the purposes of the present invention.

The amorphous propylene-ethylene copolymer (a) is completely soluble in xylene at room temperature. The amorphous propylene copolymer may also be an amorphous propylene-ethylene-1-butene copolymer.

As with the propylene polymer matrix, the dispersed phase may be unimodal or multimodal, such as bimodal.

In one embodiment, the dispersed phase is unimodal. More particularly, the dispersed phase is preferably unimodal with respect to intrinsic viscosity and/or comonomer distribution.

For the definition of unimodal and multimodal (e.g. bimodal), reference is made to the above definition.

Preferably, the monomodal dispersed phase is prepared in a single reaction stage, more preferably in a gas phase reactor, and comprises, for example, one propylene-ethylene copolymer fraction.

Final heterophasic propylene copolymer

As mentioned above, the heterophasic propylene copolymer according to the present invention is produced by sequential polymerization. Preferably, the propylene homopolymer matrix is produced in at least one step and in a subsequent step the amorphous propylene-ethylene copolymer (a) is produced in the presence of a propylene homopolymer.

In order to characterize the matrix phase and the amorphous phase of heterophasic propylene copolymers several methods are known.

The crystalline fraction and the soluble fraction can be separated by the CRYSTEX QC method using 1,2, 4-Trichlorobenzene (TCB) as solvent. The method is described in the measurement methods section below. In this process, the Crystalline Fraction (CF) and the Soluble Fraction (SF) are separated from one another. The Crystalline Fraction (CF) mainly corresponds to the matrix phase and contains only a small portion of the elastomer phase, while the Soluble Fraction (SF) mainly corresponds to the elastomer phase and contains only a small portion of the matrix phase.

Preferably, the matrix phase is at least partially crystalline, thereby ensuring that the polymer as a whole comprises both crystalline and amorphous phases.

Desirably, the matrix component is an isotactic polypropylene matrix component. The matrix component may consist of a single propylene homopolymer, but may also comprise a mixture of different propylene homopolymers. However, a single propylene homopolymer is desirably present.

The matrix component may have a melting point (Tm) of 156 to 162 ℃, preferably 158 to 161 ℃.

The melting point (Tm) of the heterophasic propylene copolymer is preferably from 156 to 162 ℃, preferably from 157 to 161 ℃, especially from 158 to 161 ℃.

It is preferred that the heterophasic propylene copolymer has an MFR2 of from 0.1 to 10g/10min, such as from 0.1 to 5.0g/10 min.

Preferably, the heterophasic propylene copolymer has a xylene soluble fraction of from 5.0 to 30 wt%.

Preferably, the heterophasic propylene copolymer comprises from 50.0 to 95.0 wt% of Crystalline Fraction (CF), especially from 70.0 to 95.0 wt%.

Preferably, the heterophasic propylene copolymer comprises from 5.0 to 50.0 wt% of Soluble Fraction (SF), especially from 5.0 to 30.0 wt% of soluble fraction.

Preferably, the ethylene content of the soluble fraction is from 18.0 to 55.0 wt%, preferably from 20.0 to 50.0 wt%.

Preferably the heterophasic propylene copolymer has an Mw/Mn from 1.0 to 4.0.

Applications of the invention

The heterophasic polypropylene resin of the present invention may be used for the manufacture of articles such as flexible pipes/tubes, profiles, cable insulation, sheets or films. These articles can be used in the medical and general packaging fields, as well as for technical applications such as power cables or geomembranes. Alternatively, the heterophasic polypropylene resin may be used for impact modification of compositions for injection molding of articles, for example for technical applications in the automotive field.

For impact modification, the heterophasic polypropylene resin of the present invention may be blended with another polypropylene resin. Accordingly, the present invention also relates to a polymer blend comprising the heterophasic polypropylene resin of the present invention.

The polymers of the present invention can be used to make a variety of end articles, such as films (cast, blown or BOPP films), molded articles (e.g., injection molded, blow molded, rotomolded articles), extrusion coatings, and the like. Preferably, the articles comprising the films of the present invention are used in packaging. Packaging of interest includes heavy duty bags, hygiene films, laminated films and flexible packaging films.

The invention will now be illustrated by reference to the following non-limiting examples.

Analytical testing

The measuring method comprises the following steps:

measurement of Al, Zr and Hf (ICP method)

In a glove box, an aliquot of the catalyst (about 40 mg) was weighed onto a glass weigh boat using an analytical balance. The sample was then exposed to air overnight while it was placed in a steel secondary container equipped with an air inlet. The boat contents were then rinsed into an Xpress microwave vessel (20 mL) with 5 mL of concentrated nitric acid (65%). The samples were then subjected to microwave-assisted digestion using a MARS 6 laboratory microwave apparatus at 150 ℃ for 35 minutes. The digested sample was cooled for at least 4 hours and then transferred to a glass volumetric flask of 100mL volume. A standard solution containing 1000mg/L Y and Rh (0.4mL) was added. The flask was then filled with distilled water and shaken well. The solution was filtered through a 0.45 μm nylon needle filter and then analyzed using Thermo iCAP 6300ICP-OES and iTEVA software.

Use blank (5% HNO)₃0.005Mg/L, 0.01Mg/L, 0.1Mg/L, 1Mg/L, 10Mg/L and 100Mg/L of Al, B, Hf, Mg, Ti and Zr at 5% HNO with six standards₃The instrument was calibrated for Al, B, Hf, Mg, Ti and Zr in solution in distilled water. However, not every calibration point is used for every wavelength. Each calibration solution contained 4mg/L of Y and Rh standards. The Al 394.401nm was calibrated using the following calibration points: blank, 0.1mg/L, 1mg/L, 10mg/L and 100 mg/L. Use blank, 0.01mg/L, 0.1mg/L, 1mg/L, 10mg/L and 100mg/L, Al 167.079nm was calibrated to Al 394.401nm, excluding 100mg/L and Zr339.198nm. The calibration curve uses curve fitting and 1/concentration weighting. Blank, 0.01mg/L, 0.1mg/L, 1mg/L, 10mg/L and 100mg/L standards were used to calibrate Hf 264.141 nm.

Immediately prior to analysis, the calibration was verified and adjusted (instrument slope function) using a blank and 10Mg/L Al, B, Hf, Mg, Ti and Zr standards with 4Mg/L Y and Rh. Quality control samples (QC: 1Mg/LAl, Au, Be, Hg, and Se; 2Mg/L Hf and Zr, 2.5Mg/L As, B, Cd, Co, Cr, Mo, Ni, P, Sb, Sn, and V; 4Mg/L Rh and Y; 5Mg/L Ca, K, Mg, Mn, Na, and Ti; 10Mg/L Cu, Pb, and Zn; 25Mg/L Fe and 37.5Mg/L Ca at 5% HNO ₃Distilled water solution of (c) to confirm the reset slopes of Al, B, Hf, Mg, Ti and Zr. QC samples were also run at the end of the predetermined analysis set.

The Zr content was monitored using a Zr 339.198nm {99} line. Hf 264.141nm {128} line was used to monitor the Hf content. The aluminum content was monitored by 167.079nm {502} line when the Al concentration in the test portion was below 2 wt%, and by 394.401nm {85} line when the Al concentration was above 2 wt%. Y371.030 nm {91} was used as internal standard for Zr 339.198nm and Al 394.401nm, Y224.306 nm {450} was used for Al 167.079 nm.

The reported values were back-calculated to the original catalyst sample using the original mass and dilution volume of the catalyst aliquot.

GPC: average molecular weight, molecular weight distribution and polydispersity index (Mn, Mw/Mn)

Average molecular weights (Mw and Mn), Molecular Weight Distribution (MWD), and their breadth (described by polydispersity index), PDI-Mw/Mn (where Mn is the number average molecular weight, and Mw is the weight average molecular weight) were determined by Gel Permeation Chromatography (GPC) according to ISO 16014-1:2003, ISO16014-2:2003, ISO 16014-4:2003, and ASTM D6474-12.

A high temperature GPC instrument equipped with an Infrared (IR) detector (IR 4 or IR5 from PolymerChar, spain) or a differential Refractometer (RI) from Agilent technologies, 3 Agilent-PLgel oxygen columns and 1 Agilent-PLgel oxygen Guard column was used. 1,2, 4-Trichlorobenzene (TCB) stabilized with 250mg/L of 2, 6-di-tert-butyl-4-methylphenol was used as solvent and mobile phase. The chromatography system was operated at 160 ℃ and a constant flow rate of 1 mL/min. 200 μ L of sample solution was injected for each analysis. Data collection was performed using Agilent Cirrus software version 3.3 or PolymerChar GPC-IR control software.

The column set was calibrated using a universal calibration method (according to ISO 16014-2:2003) using 19 narrow MWD Polystyrene (PS) standards in the range of 0.5kg/mol to 11500 kg/mol. PS standards were allowed to dissolve for several hours at room temperature. The conversion of polystyrene peak molecular weight to polyolefin molecular weight is accomplished by using the Mark-Houwink (Mark Houwink) equation and the following Mark-Houwink (Mark Houwink) constants:

K_PS＝19x10^-3mL/g，α_PS＝0.655

K_PE＝39x10^-3mL/g，α_PE＝0.725

K_PP＝19x10^-3mL/g，α_PP＝0.725

a third order polynomial fit is used to fit the calibration data.

All samples were prepared at concentrations in the range of 0.5-1mg/ml and dissolved at 160 ℃ for 2.5 hours (for PP) or 3 hours.

DSC analysis

DSC analysis was performed on 5 to 7mg samples using Mettler TA instruments Q2000 Differential Scanning Calorimetry (DSC). DSC was run according to ISO 11357/part 3/method C2 at a heating/cooling/heating cycle with a scan rate of 10 ℃/min over a temperature range of-30 ℃ to +225 ℃. The crystallization temperature (Tc) is determined by the cooling step, while the main melting temperature (Tm) and the heat of fusion (H)_m) Determined by the second heating step.

Melt flow rate

The Melt Flow Rate (MFR) is determined according to ISO 1133 and is expressed in g/10 min. MFR is an indication of the flowability and processability of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. MFR was determined at 230 ℃ and a load of 2.16kg (MFR 2).

Determination of xylene soluble fraction (XS):

the xylene soluble fraction (XS) as defined and described in the present invention is determined according to ISO 16152 as follows: 2.0g of polymer are dissolved in 250ml of p-xylene at 135 ℃ with stirring. After 30 minutes, the solution was allowed to cool at ambient temperature for 15 minutes and then allowed to stand at 25 ± 0.5 ℃ for 30 minutes. The solution was filtered with filter paper into two 100ml flasks. The solution from the first 100ml vessel was evaporated in a nitrogen stream and the residue was dried under vacuum at 90 ℃ until a constant weight was reached. The xylene soluble fraction (weight percent) can then be determined as follows:

XSwt％＝(100x m1 x v0)/(m0 x v1),

where m0 denotes the initial polymer amount (g), m1 defines the weight of the residue (g), v0 defines the initial volume (ml), and v1 defines the volume of the sample analyzed (ml).

CRYSTEX

Crystalline and soluble fractions and their respective properties

Polypropylene (PP) compositions were analyzed for Crystalline (CF) and Soluble Fractions (SF) as well as comonomer content and intrinsic viscosity of each fraction by CRYSTEX QC, Polymer Char (valencia, spain).

Schematic of CRYSTEX QC instrument see Del hirrro, p.; orin, a.; montabal, b.; analysis of soluble fraction in polypropylene, special column, 2 months 2014, pages 18-23. The crystalline and amorphous fractions were separated by temperature cycling of dissolution at 160 ℃, crystallization at 40 ℃ and redissolution in 1,2, 4-trichlorobenzene (1,2,4-TCB) at 160 ℃. Quantification of SF and CF and determination of ethylene content (C2) were performed by an infrared detector (IR4) and an online dual capillary viscometer for Intrinsic Viscosity (IV).

The IR4 detector is a detector for detecting two different wavelength bands (CH)₃And CH₂) A multi-wavelength detector of IR absorbance at the bottom for determining the concentration and ethylene content of the ethylene-propylene copolymer. The IR4 detector was calibrated using a series of EP copolymers where the ethylene content was known to be in the range of 2 to 69 wt% (determined by 13C-NMR).

The amount of Soluble Fraction (SF) and Crystalline Fraction (CF) is related by XS calibration to the amount of "xylene cold soluble" (XCS) and Xylene Cold Insoluble (XCI) fraction determined by standard gravimetric method according to ISO 16152. XS calibration was achieved by testing various EP copolymers having XS content in the range of 2-31 wt%.

The Intrinsic Viscosity (IV) of the parent EP copolymer and its soluble and crystalline fractions was determined using an online dual capillary viscometer and correlated with the corresponding IV determined by assay according to ISO 1628 in decalin.

Calibration was achieved using several commercial EP PP copolymers with IV ranging from 2 to 4 dL/g.

Samples of the PP composition to be analyzed are weighed out at a concentration of 10mg/ml to 20 mg/ml. After the vials were automatically filled with 1,2,4-TCB containing 250mg/l of 2, 6-tert-butyl-4-methylphenol (BHT) as antioxidant, the samples were dissolved at 160 ℃ with continuous stirring at 800rpm until complete dissolution (typically over 60 minutes).

A defined volume of sample solution is injected into a chromatographic column filled with an inert carrier, where crystallization of the sample and separation of the soluble fraction from the crystallized fraction is performed. This process was repeated twice. During the first injection, the whole sample was measured at elevated temperature to determine the IV [ dl/g ] and C2[ wt. ]ofthe PP composition. During the second injection, the soluble fraction (at low temperature) and the crystalline fraction (at high temperature) accompanying the crystallization cycle were measured (wt% SF, wt% C2, IV).

Examples

Metallocene synthesis

Chemicals used for complex preparation:

2, 6-dimethylaniline (Acros), 1-bromo-3, 5-xylene (Acros), 1-bromo-3, 5-di-tert-butylbenzene (Acros), bis (2, 6-diisopropylphenyl) imidazolium chloride (Aldrich), triphenylphosphine (Acros), NiCl2(DME) (Aldrich), dichlorodimethylsilane (Merck), ZrCl4(Merck), trimethyl borate (Acros), Pd (OAc)2(Aldrich), NaBH4(Acros), 2.5M nBuLi hexane solution (Chemeal), CuCN (Merck), magnesium turnip (Acros), silica gel 60, 40-63 μ M (Merck), bromine (Merck), 96% sulfuric acid (Reachim), sodium nitrite (Merck), copper powder (Alfa), potassium hydroxide (Merck), K2CO3(Merck), 12M OH (Mercym), Na (Aldrich), MgSO 82 (MgSO) Na (Alck), Na2CO 2 (Merck), diethyl ether (Mercek), methanol (Mgo) 2 (Merck), NaCl (GCO 5932), methanol (Merck), NaCl) (Acrok), NaCl (Merck), NaCl) (2M 365932) 2 (Merck), sodium nitrite (Merck), and sodium nitrite (Merck) 1, 2-dimethoxyethane (DME, Aldrich), 95% ethanol (Merck), dichloromethane (Merck), hexane (Merck), THF (Merck), and toluene (Merck) were used as received. Hexane, toluene and dichloromethane for organometallic synthesis were dried over molecular sieve 4a (merck). Diethyl ether, THF and 1, 2-dimethoxyethane used for organometallic synthesis were distilled over sodium benzophenone ethyl. CDCl3(Deutero GmbH) and CD2Cl2(Deutero GmbH) were dried over molecular sieves 4A.

4, 8-dibromo-1-methoxy-2-methyl-1, 2,3,5,6, 7-hexahydro-s-indacene and 5-tert-butyl-7- (3, 5-di-tert-butylphenyl) -6-methoxy-2-methyl-1H-indene were obtained as described in WO 2015/158790.

Synthesis of MC1 (metallocene of the invention)

4, 8-bis (3, 5-dimethylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-indacene

To a volume of 2.0g (2.56mmol) of NiCl₂(PPh₃) To a mixture of IPr and 36.3g (100.8mmol) of 4, 8-dibromo-1-methoxy-2-methyl-1, 2,3,5,6, 7-hexahydro-s-indacene was added 500ml (250mmol, 2.5 equiv.) of a solution of 3, 5-dimethylphenylmagnesium bromide in 0.5M THF at a rate to maintain a gentle reflux (for about 15 minutes). The resulting solution was refluxed for an additional 1 hour, then cooled to room temperature and 1200ml of 0.5M HCl and 500ml of dichloromethane were added. Separating the organic layer at K₂CO₃Dried on silica gel 60 short pad (40-63 μm, ca. 30ml) and then evaporated to dryness to give a crude mixture of diastereomers of 4, 8-bis (3, 5-dimethylphenyl) -1-methoxy-2-methyl-1, 2,3,5,6, 7-hexahydro-s-indacene as a brown oil. Still further, 315mg of TsOH was added to a solution of the crude product in 420ml of toluene, and the resulting mixture was refluxed for 10 minutes using a Dean-Stark head. Then, a further portion of 220mg TsOH was added and the resulting mixture was refluxed for 10 minutes. Finally, the last operation was repeated with 50mg of TsOH. After cooling to room temperature, 200ml of 10% K are used ₂CO₃The reaction mixture was washed. Separating the organic layer and using it additionallyThe aqueous layer was extracted with 200ml dichloromethane. Allowing the combined organic extracts to stand in anhydrous K₂CO₃The organic layer was dried (at this stage, the organic layer turned dark red), passed through a short pad of silica gel 60 (40-63 μm, 30ml), and the resulting pale yellow solution was evaporated to about 30ml, yielding a solution containing a large amount of white precipitate. To the mixture was added 300ml of n-hexane. The precipitated solid (G3) was filtered off, washed with n-hexane and dried in vacuo. This procedure yielded 29.33g (77.48mmol, 76.9%) of 4, 8-bis (3, 5-dimethylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-indacene as a white fine crystalline solid. The mother liquor was evaporated to dryness to give a pale yellow solid block. The solid mass was triturated with 40ml of warm n-hexane, cooled to room temperature and filtered (G3). The resulting solid was washed with n-hexane and dried under vacuum. This procedure additionally gave 4.55g (12.02mmol, 11.9%) of 4, 8-bis (3, 5-dimethylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-indacene as a white powder. Thus, the total yield of the title product was 33.88g (89.5mmol, 88.8%).

¹H NMR(CDCl₃)：δ7.04(s,2H),7.03(s,2H),6.98(s,2H),6.43(m,1H),3.23(s,2H),2.89(t,J＝7.3Hz,2H),2.83(t,J＝7.3Hz,2H),2.38(s,6H),2.37(s,6H),2.04(s,3H),1.99(quint，J＝7.3Hz,2H)。¹³C{¹H}NMR(CDCl₃)：δ145.38,142.84,140.85,140.43,140.21,139.80,138.37,137.55,137.39,133.44,129.64,128.39,128.19,127.31,126.61,126.34,42.49,32.76,32.51,26.08,21.43,16.81。

[4, 8-bis (3, 5-dimethylphenyl) -2-methyl-1, 5,6, 7-tetrahydro-s-indacen-1-yl ] chlorodimethylsilane

A suspension of 11.96g (31.59mmol)4, 8-bis (3, 5-dimethylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-indacene in a mixture of 250ml diethyl ether and 40ml THF is cooled to-30 ℃ and 13.0ml (31.59mmol) 2.43M are added in one portionⁿBuLi in hexane solution. The resulting mixture was stirred at room temperature overnight and the light orange solution thus obtained containing a large amount of orange precipitate was then cooledIt was cooled to-50 ℃ and 19.0ml (20.33g, 157.5mmol, 4.99 equivalents) of dichlorodimethylsilane were added in one portion. The mixture was stirred at room temperature overnight, then filtered through a frit (G3), and the flask and filter cake were rinsed with 50ml of toluene. The filtrate was evaporated to dryness to give 14.9g (. about.100%) of the title compound as a white solid block, which was used further without additional purification.

¹H NMR(CDCl₃): δ 7.09(s,2H),7.02-6.94(m,4H),6.51(m,1H),4.07(s,1H),3.26-3.14(m,1H),2.95-2.79(m,2H),2.60(ddd, J ═ 12.4Hz, J ═ 8.4Hz, J ═ 4.1Hz,1H),2.38 and 2.37(2s, sum 12H),2.24(s,3H),2.12-1.99(m,1H),1.95-1.80(m,1H), -0.16(s,3H), -0.20(s, 3H).¹³C{¹H}NMR(CDCl₃)：δ146.19,143.17,140.68,140.29,139.94,139.92,138.37,137.59,137.42,132.60,129.86,128.52,128.24,127.85,127.28,126.32,49.67,33.33,32.73,26.15,21.45,21.42,18.10,3.92,-1.45。

[4, 8-bis (3, 5-dimethylphenyl) -2-methyl-1, 5,6, 7-tetrahydro-s-indacen-1-yl ] [ 6-tert-butyl-4- (3, 5-dimethylphenyl) -5-methoxy-2-methyl-1H-inden-1-yl ] dimethylsilane

A solution of 10.13g (31.59mmol) of 5-tert-butyl-7- (3, 5-dimethylphenyl) -6-methoxy-2-methyl-1H-indene (produced as described above for MC-1) in 250ml of diethyl ether was cooled to-30 ℃ and 13.0ml (31.59mmol) of 2.43M 2M were added in one portionⁿBuLi in hexane solution. The mixture was stirred at room temperature overnight, then the resulting light orange solution containing a small amount of precipitate was cooled to-45 ℃ and 200mg of CuCN was added. The resulting mixture was stirred at-25 ℃ for 0.5 h, then 14.9g (31.59mmol [4, 8-bis (3, 5-dimethylphenyl) -2-methyl-1, 5,6, 7-tetrahydro-s-indacen-1-yl) were added in one portion]A solution of chlorodimethylsilane (prepared as above) in 200ml THF. The mixture was stirred at room temperature overnight and then filtered through a short pad of silica gel 60 (40-63 μm) and washed with 2X50 ml of dichloromethane. The combined organic eluates are evaporated to dryness and the residue is dried under vacuum at elevated temperature24.0g (about 100% or about 90% purity) of the title product are obtained as a pale yellow solid foam (about 55:45 mixture of stereoisomers), which is used further without additional purification.

¹H NMR(CDCl₃): δ 7.27 and 7.25(2s, sum 2H),7.04(s,4H),6.98,6.95 and 6.93(3s, sum3H),6.90 and 6.85(2s, sum1H), 6.46(s,1H),6.23 and 6.20(2s, sum1H), 4.41 and 4.16(2s, sum1H),3.30-2.62(m,1H),3.22 and 3.20(2s, sum3H), 3.04-2.79(m,2H),2.68-2.56(m,1H),2.39(s,6H),2.35(s,9H),2.32(s,3H),2.18-1.80(6s and 2m, sum 9H),1.44 and 1.38(2s, sum 2H), 2.32(s,3H), -0.52-0.73, -0.52 (s, sum 3H).

Trans-dimethylsilanediyl [ 2-methyl-4, 8-bis (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl ] zirconium dichloride (MC1) obtained without an epimerization step

Will be provided withⁿBuLi Hexane solution (2.43M,24.8ml,60.26mmol) was added in one portion to pale yellow [ 2-methyl-4, 8-bis (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl][ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl]Dimethylsilane (22.76g, 30.14mmol, assuming 100% purity) in 250ml of ether solution (cooled to-50 ℃). The mixture was stirred at room temperature for 5.5 hours, then the resulting dark red solution was cooled to-50 ℃ and HfCl was added₄(9.66g,30.16 mmol). The reaction mixture was stirred at room temperature for 24 hours to give a red solution with some LiCl precipitation. The mixture was evaporated to dryness (to a red foam state) and the residue was treated with 100ml warm toluene. The resulting suspension was filtered through a frit (G4), the filtrate was evaporated to about 25ml, and 25ml of n-hexane was added. The resulting mixture was filtered again through a frit (G4) and the resulting filtrate was evaporated to dryness. The residue was purified by crystallization from a mixture of 25ml of n-hexane and 25ml of n-pentane, followed by crystallization from 30ml of pure pentane. This process is subject to several reactions The ratio of the complex of formula (I) to the complex of cis varying from 70/30 to 90/10. The total weight of all products was 13.1 grams, corresponding to a trans/cis complex mixture yield of about 43.5%. It is difficult to completely purify such metallocene isomer mixtures due to the presence of impurities. It is also not possible to separate the pure trans isomer from the resulting mixture.

Trans-dimethylsilanediyl [ 2-methyl-4, 8-bis (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl ] zirconium dichloride (MC1) obtained by an epimerisation step

Will be provided withⁿBuLi Hexane solution (2.43M,32.2ml,78.25mmol) was added in one portion to pale yellow [ 2-methyl-4, 8-bis (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl][ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl]Dimethylsilane (29.5g,39.07mmol, 95% purity, prepared as described above) was added to 250ml of diethyl ether solution (cooled to-50 ℃). The mixture was stirred at room temperature for 5.5 hours, then the resulting dark red solution was cooled to-50 ℃ and HfCl was added₄(12.52g,39.09 mmol). The reaction mixture was stirred at room temperature for 24 hours to give a red solution containing a LiCl precipitate. The mixture was evaporated to dryness, 150ml of THF was added to the residue, and the resulting mixture was heated at 65 ℃ for 24 hours. The mixture thus obtained is evaporated to dryness, the residue is dissolved in 100ml of warm toluene, the suspension thus obtained is filtered through a frit (G4), and the filter cake is washed with 10ml of toluene. The solution was evaporated to dryness and the residue was dissolved in 50ml of hot n-hexane. The yellow fine crystalline solid precipitated from the solution at room temperature was collected and dried in vacuo. This procedure gave 16.6 g of trans-hafnocene dichloride containing about 1.1mol of n-hexane per mol of complex (or an amount of 1.4g of n-hexane), so that the net weight of the trans-complex isolated after adjustment was 15.2g (39%). The mother liquor was evaporated to dryness and the residue was dissolved in 60ml of n-pentane. At-30 deg.C from the The yellow powder which precipitates out of the solution over several days is filtered off (G4) and then dried in vacuo to give 9.4G of the target trans complex, contaminated with about 5% of the unknown complex and containing about 0.6 equivalents of n-hexane per equivalent of the target complex. The total isolated pure trans-MC 1 corresponded to an isolated yield of 62%.

Synthesis of MCC

Trans-dimethylsilanediyl [ 2-methyl-4, 8-bis (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl ] zirconium dichloride (MCC)

To a solution of 23.06g (30.54mmol) of [4, 8-bis (3, 5-dimethylphenyl) -2-methyl-1, 5,6, 7-tetrahydro-s-indacen-1-yl][ 6-tert-butyl-4- (3, 5-dimethylphenyl) -5-methoxy-2-methyl-1H-inden-1-yl]To a slightly turbid, pale yellow solution of dimethylsilane in 250ml of diethyl ether (cooled to-30 ℃) were added in one portion 25.1ml (60.99mmol) of 2.43MⁿBuLi in hexane. The mixture was stirred at room temperature for 5.5 hours, then the resulting red solution was cooled to-50 ℃ and 7.12g (30.55mmol) ZrCl was added₄. The reaction mixture was stirred at room temperature for 24 hours to give a deep red solution containing a LiCl precipitate. According to the nmr spectrum, the solution contains a mixture of trans-zirconocene dichloride and cis-zirconocene dichloride of about 85/15, which contains some other impurities. The mixture was evaporated to dryness (to a red foam) and the residue was treated with 100ml warm toluene. The resulting suspension was filtered through a frit (G4) and the filter cake was washed with 2x50 ml warm toluene. The filtrate was evaporated to dryness and the residue was dissolved in 70ml of hot n-hexane. The light orange precipitate that fell from the solution overnight at room temperature was collected and dried in vacuo. This procedure yielded 7.8g of trans-dimethylsilanediyl [ 2-methyl-4, 8-bis (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ][ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl]Zirconium dichloride, containing about 1.0mol of n-hexane per mole of complex, was adjusted accordinglyThe dry weight of the isolated trans complex after completion was 7.13g (26%). The mother liquor was evaporated to about 60 ml. The light orange powder precipitated from the solution overnight at-25 ℃ was collected and dried in vacuo. This procedure yielded 8.6g of trans-dimethylsilanediyl [ 2-methyl-4, 8-bis (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl][ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl]Zirconium dichloride, containing about 0.75mol of n-hexane per mole of complex (or 0.57g of n-hexane in 8.6g of product), thus adjusted to a dry weight of 8.03g (29%) of the isolated trans complex. Thus trans-dimethylsilanediyl [ 2-methyl-4, 8-bis (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl][ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl]The total isolated yield of zirconium dichloride was only 55%. Trans-dimethylsilanediyl [ 2-methyl-4, 8-bis (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl][ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl ]Zirconium dichloride x1.0 n-hexane.

C₅₄H₆₀Cl₂OSiZr x C₆H₁₄The analytical calculation of (c): c, 71.96; h, 7.45. Measured value: c, 72.30; h, 7.69.

¹H NMR(CDCl₃): δ 7.55-6.90 (very wide singlet, 4H),7.39(s,1H),7.10(s,1H),7.03(s,1H),6.98(s,1H),6.95(s,1H),6.94(s,1H),6.81(s,1H),6.58(s,1H),3.41(s,3H),3.15-3.01(m,2H),2.93(ddd, J ═ 16.0Hz,8.1Hz,3.3Hz,1H),2.51-2.41(m,1H),2.39(s,3H),2.36(s,3H),2.34(s,12H),2.30(s,3H),2.04(s,3H),2.07-1.95(m,1H),1.85-1.68(m,1H),1.35(s, 1H), 13.13H, 13H, 1H, 2.85, 1H, 2.6H, 13H, 1H, 13H, 2H, 13H, 2.6H, 13H, 2H, 2.6H, 13H, 1H, 2.6H, 2.h, 2, 2.6H, 2H, 2H, 2H, 2H, 2H, 2H, 2, and the like.¹³C{¹H}NMR(CDCl₃): δ 159.87,144.73,144.10,143.25,141.39,138.39,138.08,137.81,137.47,136.90,134.61,134.39,134.26,132.05,131.96,131.74,131.11,128.96,128.91,128.82,128.74,127.74,127.44,127.01 (broad singlet), 126.76,123.42,123.12,121.60,121.08,82.55,81.91,62.67,35.68,33.87,32.39,30.39,26.04,21.53,21.47,21.41,21.24,19.78,18.60,3.62, 1.70.

Alternative synthesis with improved epimerization process

Embodiments of the present invention for MCC

Step 1: synthesis of metallocene complex trans-isomer and cis-isomer mixture in di-n-butyl ether

At room temperatureⁿBuLi in hexane solution (8.7ml,2.43M,21.14mmol) was added in one portion to 8.0g (10.59mmol) of [4, 8-bis (3, 5-dimethylphenyl) -2-methyl-1, 5,6, 7-tetrahydro-s-indacen-1-yl ][ 6-tert-butyl-4- (3, 5-dimethyl-phenyl) -5-methoxy-2-methyl-1H-inden-1-yl]100ml of dimethylsilane (purity about 88%)ⁿBu₂O in a light yellow solution. The mixture was stirred at room temperature for 17 hours to give a red solution, then 2.47g (10.6mmol) of ZrCl₄Adding into the mixture. The reaction mixture was stirred at room temperature for 24 hours to give a red solution with a yellow precipitate. The mixture comprised a mixture of about 85/15 trans and cis zirconium dichloride with some impurities as evidenced by nuclear magnetic resonance spectroscopy. The reaction mixture was evaporated to dryness. The residue was dissolved in 60ml of toluene and the resulting mixture was filtered through a frit (G4). The filtrate was evaporated to dryness and the precipitate was dissolved in 30ml of n-hexane. An orange powder precipitated from the solution overnight at-25 ℃ and was collected and dried in vacuo. This procedure yielded 7.2g of an about 80:12 mixture of trans and cis zirconium dichlorides with an impurity content of about 8% and containing about 0.76mol of n-hexane per mole of complex (or 7.2g of product containing 0.48g of n-hexane). Thus, the net weight of the adjusted trans and cis mixtures of zirconium dichloride was about 6.72g (69%).

This synthesis was repeated in di-n-butyl ether at lower and higher temperatures, respectively, to give the results shown in the table below.

Temperature, C	Isolated yield of trans/cis mixture, wt.%	Trans/cis ratio
			0	76	83:17
23	69	85:15
			60	61	82:18

Step 2: epimerization

2.1 epimerization with LiCl-THF

To 1.80g (1.97mmol) of the synthesized orange powder was added LiCl (300mg) and THF (20ml) at room temperature, and the resulting mixture was stirred at 65 ℃ for 20 h. The reaction temperature was then raised to 80 ℃ and stirring continued at this temperature. The epimerization proceeds by¹H NMR spectroscopy was monitored and the results are given in the following table:

time, h	Temperature, C	Trans/cis ratio	Organic metal impurities,% of
				0 (initial ratio)		About 80:12	8
20	65	About 87:13	0
				40	80	About 90:10	0
60	80	About 92:8	0
				80	80	About 95:5	0

Thus, by this process (epimerization with LiCl in THF after synthesis) the yield and purity of the trans isomer can be significantly improved and purification of the trans isomer can be facilitated (trans/cis ratio higher than 99:1 can be achieved with only one crystallization).

2.2 epimerization with TEABAC

TEABAC (10.0g,43.9mmol) andⁿBu₂o (170ml) was added to 27.5g of cis-and trans-dimethylsilanediyl [ 2-methyl-4, 8-bis (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl][ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl]The trans/cis ratio in the mixture of zirconium dichloride (MCC) was about 85: 15. The resulting mixture was stirred at 120 ℃ for 70 hours. The mixture is then evaporated To dryness, the residue was dissolved in 150ml of toluene and the suspension was heated to 80 ℃ for 20 minutes and then filtered through a frit (G4). According to¹Evidence of H NMR spectroscopy yielded a filtrate containing a mixture of trans and cis zirconium dichloride in a trans/cis ratio of 97:3, containing about 10% impurities.

The filtrate was evaporated to a high viscosity state (oil) and then dissolved in 30 ml of hot n-hexane. The resulting hot suspension was filtered through a frit. An orange powder precipitated from the filtrate at room temperature for 5 minutes was collected and dried under vacuum. This procedure gave 13.8g of trans-dimethylsilanediyl [ 2-methyl-4, 8-bis (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl][ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl]Zirconium dichloride (MCC) containing 0.1 gⁿBu₂O and 0.06 g of n-hexane.

The mother liquor was evaporated to dryness and the residue was recrystallized from 25ml of n-pentane overnight at-25 ℃. The precipitated orange powder was collected and dried in vacuo. This procedure additionally gives 2.4g of trans-dimethylsilanediyl [ 2-methyl-4, 8-bis (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl][ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl ]Zirconium dichloride (MCC) containing 17mgⁿBu₂O and 10mg of n-pentane.

Finally, the mother liquor was evaporated to dryness and the resulting orange solid was dried in vacuo. Crystallization from 15ml of n-pentane at-25 ℃ overnight gave 1.26g of trans-dimethylsilanediyl [ 2-methyl-4, 8-bis (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl ] zirconium dichloride (MCC) containing 90mg of n-pentane. Thus, the total isolated yield of pure trans isomer was 63 wt%.

₂ ₂2.3 epimerization with TEBAC in CHCl

TEAC (24mg,0.105mmol,20 mol.%) and 2ml CH₂Cl₂To 0.48g (0.52mmol) of trans-and cis-dimethylsilanediyl [ 2-methyl-4, 8-bis (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl][ 2-methyl-4- (3, 5-dimethylphenyl)) -5-methoxy-6-tert-butylinden-1-yl]Zirconium dichloride (MCC) in a mixture of about 85: 15. The resulting reddish homogeneous mixture was stirred at room temperature for 96 hours. Thereafter, an additional 24mg (0.105mmol, 20 mol.%, i.e. 40 mol.% total) of TEBAC was added and the reaction mixture was stirred at this temperature for 48 h. By passing¹HNMR spectroscopy monitored the progress of isomerization (results are listed below).

Time, h	Trans/cis ratio
		0 (initial ratio)	About 85/15
24	About 89/11
		96	About 91/9
144*	About 95/5

96 hours later additional TEBAC was added

With dimethylsilanediyl [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl][ 2-methyl-4- (3, 5-dimethylphenyl) -5,6, 7-trihydro-s-indacen-1-yl]Zirconium dichloride (MC)_Reference) Comparative example (2)

Step 1: in di-n-butyl ether MC_ReferenceSynthesis of a mixture of trans and cis isomers

At room temperatureⁿBuLi in hexane solution (12.4ml,2.43M,30.13mmol) was added in one portion to 9.77g (15.01mmol) of [ 6-tert-butyl-4- (3, 5-dimethylphenyl) -5-methoxy-2-methyl-1H-inden-1-yl][4- (3, 5-dimethylphenyl) -2-methyl-1, 5,6, 7-tetrahydro-s-indacen-1-yl]125ml of dimethylsilane (obtained as described in WO2018/122134, purity about 94%)ⁿBu₂O in a light yellow solution. The mixture was stirred at room temperature for 17 hours to give a red solution, which was cooled in an ice bath. Then, 3.5g (15.02mmol) of ZrCl was added thereto₄. The reaction mixture was stirred at room temperature for 24 hours to give an orange solution with an orange precipitate. According to¹As evidenced by the H NMR spectrum, the mixture comprised a mixture of about 1:1 trans and cis zirconium dichloride with some impurities. The reaction mixture was partially evaporated to remove most of the hexane (about 15ml of solvent distilled off in total).

And 2, step: epimerization

TEBAC (3.50g,15.37mmol) was added to the residue and the resulting mixture was stirred at 120 ℃ for 48 h. The reaction mixture is then evaporated to dryness, the residue is heated with 100ml of toluene and the hot suspension obtained is filtered through a frit (G4). According to¹Evidence of H NMR spectroscopy the filtrate contained a mixture of trans and cis zirconium dichloride, about 60:40, which contained some impurities.

Preparation of MAO-silica support

A steel reactor equipped with a mechanical stirrer and a filter screen was flushed with nitrogen and the reactor temperature was set to 20 ℃. Next, a pre-calcined silica grade DM-L-303(7.4kg) at 600 ℃ from AGC Si-Tech Co was added from a feed cylinder, then carefully pressurized using a manual valve and depressurized with nitrogen. Toluene (32.2kg) was then added. The mixture was stirred (40rpm) for 15 minutes. A30 wt.% solution of MAO in toluene (17.5kg) from Lanxess was then added over 70 minutes via a 12mm feed line at the top of the reactor. The reaction mixture was then heated to 90 ℃ and stirred at 90 ℃ for a further two hours. The slurry was allowed to settle and the mother liquor was filtered off. The solid was washed twice with toluene (32.2kg) at 90 ℃ and then settled and filtered. The reactor was cooled to 60 ℃ and the solid was washed with heptane (32.2 kg).

Finally, the solid was dried at 60 ℃ for 2h under a stream of nitrogen at 2kg/h, a pressure of 0.3 bar (barg) and then under vacuum (-0.5 bar (barg)) for 5 hours with stirring at 5 rpm. The solid MAO-silica support was collected as a free-flowing white powder containing 12.7 wt.% Al.

Catalyst preparation

Catalyst CE1a (comparative). In a glove box filled with nitrogen, 0.2mL of MAO (30 wt% in toluene, AXION 1330 CA Lanxess) in dry toluene (2.3mL) was added to an aliquot of metallocene MCC (24.9mg, 27. mu. mol). The mixture was stirred at room temperature for 60 minutes. Next, 2.0g of MAO treated silica prepared as described above was placed in a glass reactor equipped with a porous frit. Then a solution of metallocene and MAO in toluene was slowly added to the support over 5 minutes with gentle mixing. The resulting mixture was shaken well and left overnight. Anhydrous toluene (10mL) was then added and the slurry was mixed well with an inert gas sparged through a sieve over 10 minutes. The solid was allowed to settle and the liquid was filtered off and discarded. The resulting filter cake was dried under vacuum for 1 hour to give 1.9g of catalyst as a pink free-flowing powder.

Catalyst CE1b (comparative)

A30 wt.% MAO solution in toluene (0.7kg) was added to the steel nitrogen blanketing reactor via a burette at 20 deg.C. Toluene (5.4kg) was then added with stirring. Metallocene MCC (93g) was added from a metal cylinder and then rinsed with 1kg of toluene. The mixture was stirred at 20 ℃ for 60 minutes. Triphenylcarbeniumtetrakis (pentafluorophenyl) borate (91g) was then added from the metal cylinder, followed by rinsing with 1kg of toluene. The mixture was stirred at room temperature for 1 hour. The resulting solution was added to the stirred cake of MAO-silica support prepared as described above for more than 1 hour. The filter cake was allowed to stand for 12 hours and then at 60 ℃ and N₂Dried under air flow for 2 hours and dried under vacuum (-0.5 bar) with stirring for a further 5 hours.

A sample of dry catalyst was taken as a pink free-flowing powder containing 13.9% Al and 0.11% Zr.

Catalyst IE1a (inventive).

In a glove box filled with nitrogen, a solution of 0.2mL of MAO (30 wt% in toluene, AXION 1330 CA Lanxess) in dry toluene (2.3mL) was added to an aliquot (29.7mg, 27. mu. mol) of metallocene MC 1. The mixture was stirred at room temperature for 30 minutes. Triphenylcarbenium tetrakis (pentafluorophenyl) borate (25.6mg, 28. mu. mol) was then added to the mixture, and the mixture was stirred for 30 minutes. Next, 2.0g of the MAO-silica support prepared as described above was placed in a glass reactor equipped with a porous frit. Then a solution of metallocene and MAO in toluene was slowly added to the support over 5 minutes with gentle mixing. The resulting mixture was shaken well and left overnight. Anhydrous toluene (10mL) was then added and the slurry was mixed well with an inert gas sparged through a sieve over 10 minutes. The solid was allowed to settle and the liquid was filtered off and discarded. The resulting filter cake was dried under vacuum for 1 hour to give 1.9g of catalyst as a yellow free-flowing powder.

Table 1: catalyst summary:

(xviii) the molar ratio of boron to transition metal; calculated metallocene content in the catalyst

Polymerization:

details of the polymerization process are described below:

step 1:prepolymerization and bulk homopolymerization

A20.9L steel reactor containing 0.4 bar (barg) propylene was charged with 3950g of propylene. Triethylaluminium (0.80 ml of a 0.62 mol/l heptane solution) was injected into the reactor with an additional 240g of propylene. The solution was stirred at 20 ℃ and 250rpm for at least 20 minutes. Catalyst was injected as follows. The desired amount of solid catalyst was loaded into a 5ml stainless steel vial and then in a glove boxTop-addition another 5ml vial contained 4ml of n-heptane. The top vial was then pressurized with 5 bar (bar) of nitrogen. The catalyst feeder system was mounted on a port on the reactor lid. Immediately thereafter, 2.0 or 0.1NL of H were added in one minute by means of a mass flow controller₂(see polymerization Table). The valve between the two vials was opened and the solid catalyst was contacted with heptane under nitrogen pressure for 2 seconds and then flushed into the reactor with 340 grams of propylene. The prepolymerization was carried out at 20 ℃ for 10 minutes. At the end of the prepolymerization step, the temperature rose to 75 ℃. When the catalyst is in front only 0.1NL of H is added ₂When the internal reactor temperature reached 60 ℃, 1.9NL of H was added via mass flow controller₂. The reactor temperature was kept constant at 75 ℃ throughout the polymerization. The measurement of the polymerization time was started when the internal reactor temperature reached 2 ℃ below the set polymerization temperature.

And 2, step: gas phase ethylene-propylene copolymerization

After the bulk homopolymerization step was completed, the stirrer speed was reduced to 50rpm and the pressure was reduced to 0.4 bar (barg) by discharging the monomer. Triethylaluminium (0.80 ml of a 0.62 mol/l solution in heptane) was then injected into the reactor via a further 250 g of propylene via a steel cylinder. The pressure was then reduced again to 0.4 bar (barg) by venting the monomer. The stirrer speed was set to 180rpm and the reactor temperature was set to 70 ℃.

The reactor pressure was then increased to 20 bar (barg) by feeding the required C2/C3 gas mixture (see polymerization table), the composition of which is defined by:

wherein C is₂/C₃Is the weight ratio of the two monomers and R is their reactivity ratio. In this experiment, R was 0.44 and 0.49 for the zirconium catalysts CE1a and CE1b, respectively, and 0.38 for the hafnium catalyst IE1 a.

The temperature was kept constant by a thermostat and the pressure was fed by a mass flow controller with C corresponding to the target polymer composition ₂/C₃The gas mixture remains constant until the end of the set time for this step.

The reactor was then cooled to about 30 ℃ and volatile components flashed off. With N₂Purge reactor 3 times and once vacuum/N₂After recycling, the product was removed and dried overnight in a fume hood. 100g of the polymer were added with 0.5% by weight of Irganox B225 (acetone solution) and dried overnight in a fume hood and then dried for one hour in a vacuum drying cabinet at 60 ℃.

Table 2. example of polymerization: setting up, Pre-polymerization and transition to bulk step

Table 3. example of polymerization: bulk, transition to gas phase, and gas phase steps

Table 4. example of polymerization: results

TABLE 4 continuation

Claims

1. A metallocene complex represented by the formula (I):

each X is a sigma-ligand;

each R¹Independently are the same or may be different and are CH₂-R⁷Group, wherein R⁷Is H or straight or branched C_1-6Alkyl radical, C_3-8Cycloalkyl or C_6-10An aryl group;

each R ³And R⁴Independently are the same or can be different and are hydrogen, straight-chain or branched C_1-6Alkyl radical, C_7-20Arylalkyl radical, C_7-20Alkylaryl group, C_6-20Aryl or-OY radicals, in which Y is C_1-6A hydrocarbyl group;

R⁵is straight chain or branched C_1-6Alkyl radical, C_7-20Aralkyl radical, C_7-20Alkylaryl or C_6-20An aryl group; and

R⁶is C (R)⁸)₃Group of each R⁸Independently is a straight or branched chain C_1-6An alkyl group;

(B) Wherein one R is³Is an-OY group wherein Y is C_1-6A hydrocarbon radical at each phenyl radical4 of (a), the other two R³The group is tert-butyl; and/or

(C) Wherein one R is⁴Is an-OY group wherein Y is C_1-6A hydrocarbon radical in the 4-position of the phenyl ring, the other two R⁴The group is tert-butyl.

2. The metallocene catalyst complex of claim 1, wherein

Each X is independently a hydrogen atom, a halogen atom, C_1-6Alkoxy or R 'group, wherein R' is C_1-6Alkyl, phenyl or benzyl;

R₂si-represents Me₂Si-、Et₂Si-or (cyclohexyl) Me-Si-;

each R¹Independently are the same or may be different and are CH₂-R⁷Group, wherein R⁷Is H or straight or branched C_1-6Alkyl radical, C_6-10An aryl group;

each R²Independently is-CH ═, -CY ═ CH ₂-, -CHY-or-CY₂-a group wherein Y is C_1-4Hydrocarbyl and wherein n is 3-4;

each R³And R⁴Independently are the same or can be different and are hydrogen, straight-chain or branched C₁-C₆Alkyl or C_6-20Aryl, wherein at least one R is per phenyl³And at least one R⁴Is not hydrogen and wherein each phenyl group has at least one R³And at least one R⁴Is a hydrogen atom, and is,

R⁵is straight chain or branched C_1-6Alkyl or C_6-20An aryl group; and

R⁶is C (R)⁸)₃Group of each R⁸Independently is a straight or branched chain C₁-C₄An alkyl group.

3. The metallocene catalyst complex according to claim 1 or 2, wherein

Each X is independently chlorine, benzyl or methyl,

two R¹Are identical and are CH₂-R⁷Group, wherein R⁷Is H or straight or branched C_1-3An alkyl group, a carboxyl group,

each R²is-CH₂-a group in which n is 3 to 4,

R⁵is straight chain or branched C_1-6Alkyl or C_6-20An aryl group; and

R⁶is C (R)⁸)₃Group, R⁸Are identical and are C₁-C₂An alkyl group.

4. The metallocene complex according to any preceding claim, which is of formula (II)

Wherein each X is selected from the group consisting of chlorine, benzyl and C _1-6Sigma-ligands for alkyl groups;

R₂si-is Me₂Si or Et₂Si-；

(A) At least one R per phenyl group³And at least one R⁴Is not hydrogen and has at least one R per phenyl group³And at least one R⁴Is hydrogen; or

(C) At least one R⁴Is a-OY groupWherein Y is C_1-6A hydrocarbon radical, in the 4-position of the phenyl ring, two further R⁴The group is tert-butyl;

R⁵is straight or branched C_1-6An alkyl group;

5. The metallocene complex according to any preceding claim, which is of formula (III)

R₂si-is Me₂Si or Et₂Si-；

Each of R being other than hydrogen³Same, each non-hydrogen R⁴The same;

R³is hydrogen, straight or branched C_1-6An alkyl group;

R⁴is hydrogen, straight or branched C_1-6An alkyl group;

R⁵is straight or branched C _1-4An alkyl group; and

6. The metallocene complex according to any preceding claim, which is of the formula (IVa) to (IVd)

Wherein each X is the same and is chloro, benzyl or C_1-6Alkyl, preferably chloro, benzyl or methyl;

each R³And R⁴Independently are the same or may be different and are straight or branched C_1-6An alkyl group.

7. The metallocene catalyst complex according to any one of claims 1 to 5, wherein the complex is

Rac-trans-dimethylsilanediyl [ 2-methyl-4, 8-bis- (3',5' -dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] [ 2-methyl-4- (3',5' -dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl ] hafnium dichloride (MC-1)

Rac-trans-dimethylsilanediyl [ 2-methyl-4, 8-bis- (4' -tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] [ 2-methyl-4- (3',5' -dimethyl-phenyl) -5-methoxy-6-tert-butylinden-1-yl ] hafnium dichloride (MC-2)

Rac-trans-dimethylsilanediyl [ 2-methyl-4, 8-bis- (4 '-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] [ 2-methyl-4- (4' -tert-butylphenyl) -5-methoxy-6-tert-butylinden-1-yl ] hafnium dichloride (MC-3)

Rac-trans-dimethylsilanediyl [ 2-methyl-4, 8-bis- (3',5' -dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] [ 2-methyl-4- (3',5' -di-tert-butyl-phenyl) -5-methoxy-6-tert-butylinden-1-yl ] hafnium dichloride (MC-4)

Rac-trans-dimethylsilanediyl [ 2-methyl-4, 8-bis- (3',5' -dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] [ 2-methyl-4- (4' -tert-butylphenyl) -5-methoxy-6-tert-butylinden-1-yl ] hafnium dichloride (MC-5).

8. A catalyst system, comprising:

(i) the metallocene catalyst complex according to any one of claims 1 to 7;

(ii) a cocatalyst comprising a compound of a group 13 element.

9. The catalyst system of claim 8 comprising as cocatalyst (ii)

Alumoxane, combinations of alumoxane with alkyl aluminum, boron or borate cocatalysts, and combinations of alumoxane with boron-based cocatalysts.

10. The catalyst system according to claim 8 or 9, wherein the catalyst system is in solid form, supported on an external support.

11. The catalyst system of claim 10 supported on silica.

12. A process for the polymerization of propylene comprising reacting propylene and optionally a comonomer, in particular ethylene or 1-butene, with a catalyst as claimed in claims 8 to 11.

13. The process for the preparation of heterophasic propylene ethylene or heterophasic propylene ethylene 1-butene copolymer according to claim 12, comprising:

(I) Polymerizing propylene and optionally ethylene and/or 1-butene in the presence of a catalyst as claimed in claims 8 to 11 to form:

a1) a Crystalline Fraction (CF) comprising a propylene homopolymer or propylene copolymer matrix having up to 2 wt% comonomer as the matrix component; and

a2) a propylene-ethylene or propylene-ethylene 1-butene copolymer Soluble Fraction (SF) having a comonomer content of from 12 to 85% by weight, preferably from 15.0 to 70.0% by weight;

wherein the Crystalline Fraction (CF) represents from 30.0 to 95.0% by weight of the heterophasic propylene ethylene or heterophasic propylene ethylene 1-butene copolymer and the Soluble Fraction (SF) represents from 5.0 to 70.0% by weight, wherein the amount of Crystalline Fraction (CF) and Soluble Fraction (SF) is determined in 1,2, 4-trichlorobenzene at 40 ℃; and wherein

The Soluble Fraction (SF) of the heterophasic propylene-ethylene or heterophasic propylene-ethylene-1-butene copolymer has an intrinsic viscosity IV in decalin at 135 deg.C (SF) of 1.5 to 10dl/g, preferably 2 to 9dl/g, more preferably 4.5 to 9.0dl/g, most preferably 5.5 to 8.0 dl/g.

14. A process for preparing a heterophasic polypropylene copolymer comprising:

(i) a metallocene represented by the formula (5)

Wherein Mt is Hf;

each X is a sigma-ligand;

R¹and R^1’The same or may be different;

each R⁵And R⁶Independently is hydrogen or C_1-20Hydrocarbyl, optionally containing up to 2 silicon or heteroatoms, preferably-CH ═ CY ═ CH₂-, -CHY-or-CY₂A group which is part of a cyclic structure of 4 to 7 atoms, comprising the carbon atoms in the 5-and 6-positions of the corresponding indenyl ligand,

y isC_1-10A hydrocarbyl group;

each R³And R⁴Independently are the same or can be different and are hydrogen, straight-chain or branched C₁-C₆Alkyl, OY radicals or C ₇-₂₀Aralkyl, C_7-20Alkylaryl or C_6-20Aryl, and optionally two adjacent R³Or R⁴The groups may be part of a ring, including the phenyl carbons to which they are bonded;

R⁷is C optionally containing up to two silicon or hetero atoms_1-20A hydrocarbyl group;

R^7’is hydrogen or C_1-3A hydrocarbyl or OY group;

and only when R is^7’When different from hydrogen, R^6’Can be hydrogen;

(ii) a cocatalyst comprising a compound of a group 13 element;

Comonomer content, preferably ethylene content, (SF) from 12 to 85% by weight, preferably from 15 to 70% by weight,

wherein the amount of the Crystalline Fraction (CF) and the amount of the Soluble Fraction (SF) are determined in 1,2, 4-trichlorobenzene at 40 ℃.

15. A method of increasing the trans isomer content of a metallocene complex and a cis isomer mixture, such as a metallocene complex of formula 5,

comprising adding the mixture to a liquid phase comprising at least one ether compound at a temperature of from 0 to 200 ℃, preferably from 20 to 80 ℃, to form a solution or slurry of the mixture in the liquid phase, wherein a portion of the mixture in the liquid phase is in the form of solid particles and a portion of the mixture is dissolved in the ether;

and the trans isomer content of the mixture is increased by epimerization in the liquid phase.

16. A process for increasing the trans isomer content of a mixture of trans and cis isomers of a metallocene complex according to formula 1a by using at least one compound selected from the group consisting of R^y ₄NBr、R^y ₄Treating said mixture with an epimerization agent of the group consisting of NCl and LiCl, wherein each R^yIndependently selected from C₁-C₂₀A hydrocarbon group,

wherein formula 1a is:

mt is Zr or Hf;

each X is a sigma-ligand;

n is 1 or 2;

l is C, Si or Ge, and

two R¹The radicals, which may be identical or different, are hydrogen or C_1-20Hydrocarbyl, optionally containing up to 2 silicon or other heteroatoms, preferably C_1-8Hydrocarbyl, most preferably one R¹Is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, cyclopentyl, hexyl, octyl, another R¹Selected from methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, trimethylsilyl, phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, biphenyl, p-trimethylsilylphenyl, p-triethylsilyl, or

LR¹ ₂The group is 9-silafluorenyl;

R⁴、R⁵、R⁶、R^4’、R^5’、R^6’independently the same or may be different and is hydrogen or a hydrocarbyl group, optionally containing heteroatoms or Si atoms;

R^7’Is hydrogen or C_1-3Hydrocarbyl or OCH₃A group; and

17. The method for increasing the trans isomer content of a mixture of trans and cis isomers of a metallocene complex according to claim 16, wherein the mixture isWith R in a liquid phase comprising or consisting essentially of^y ₄NBr or R^y ₄NCl treatment

aa) at least one nonaromatic chlorinated compound, or

bb) at least one acyclic ether compound,

each R^yIndependently selected from C₁-C₂₀A hydrocarbon group.

18. The process for increasing the trans isomer content in a mixture of trans and cis isomers of a metallocene complex according to claim 17, wherein the treatment of the mixture according to aa) is carried out at a temperature below 80 ℃, preferably below 65 ℃, and wherein the treatment of the mixture according to bb) is carried out at a temperature above 100 ℃, preferably in the temperature range of 100 ℃ to 140 ℃.